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<strong>abiosus</strong> e.V.<br />
Non-Pr<strong>of</strong>it Association for the Advancement <strong>of</strong> Research on Renewable Raw Materials<br />
6 th Workshop on<br />
Fats and Oils as Renewable<br />
Feedstock for the Chemical<br />
Industry<br />
March 17-19, 2013<br />
Karlsruhe, Germany<br />
in Cooperation with:<br />
Karlsruhe Istitute <strong>of</strong> Technology (KIT)<br />
German Society for Fat Science (DGF)<br />
German Chemical Society (GDCh), Division <strong>of</strong> Sustainable Chemistry
Scientific and Organizing Committee<br />
Ursula Biermann, University <strong>of</strong> Oldenburg, Oldenburg, Germany<br />
Michael A. R. Meier, Karlsruhe Institute <strong>of</strong> Technology (KIT), Karlsruhe, Germany<br />
Jürgen O. Metzger, <strong>abiosus</strong> e.V. and University <strong>of</strong> Oldenburg, Oldenburg, Germany<br />
Acknowledgement<br />
Financial Support by the Fonds der Chemischen Industrie (FCI), BASF – The Chemical<br />
Company and by Clariant Produkte (Deutschland) GmbH is gratefully acknowledged.<br />
2
Content<br />
Program Lectures 6<br />
Posters 15<br />
<strong>Abstracts</strong> <strong>of</strong> lectures 19<br />
<strong>Abstracts</strong> <strong>of</strong> posters 55<br />
List <strong>of</strong> participants 89<br />
3
Program<br />
Lectures and Posters<br />
5
Sunday, March 17, 2013<br />
Registration<br />
Registration will be opened from 13:00 - 19:00<br />
15.45 Welcome and Opening<br />
Jürgen O. Metzger, <strong>abiosus</strong> e.V.<br />
Michael A. R. Meier, Division <strong>of</strong> Sustainable Chemistry <strong>of</strong> GDCh and<br />
KIT<br />
16.00 – 18.00 First Session<br />
Chair: Michael A. R. Meier<br />
16.00 – 16.30 Polyurethanes from renewable resources and carbon dioxide (M)<br />
L1<br />
Rolf Mülhaupt, Freiburg Materials Research Center and Institute for<br />
Macromolecular Chemistry, Freiburg, Germany<br />
16.30 – 17.00 Novel high molecular weight vinyl ether polymers based on<br />
plant oils (M)<br />
L2<br />
Samim Alam, Harjyoti Kalita, Satyabrata Samanta, Andrey<br />
Chernykh, Bret J. Chisholm, North Dakota State University, Fargo<br />
(ND), USA<br />
17.00 – 17.30 Protein engineering and application <strong>of</strong> enzymes in lipid<br />
modification (M)<br />
L3<br />
Uwe T. Bornscheuer, Institute <strong>of</strong> Biochemistry, Greifswald University,<br />
Germany<br />
17.30 – 18.00 Epicerol ® and the environmental challenges <strong>of</strong> bio-based<br />
chemistry (M)<br />
L4<br />
Thibaud Caulier, Solvay, Brussels, Belgium<br />
18.00 – 20.30 Poster Session and Opening Mixer.<br />
Posters will be displayed until the end <strong>of</strong> the workshop<br />
(M)<br />
(D)<br />
Main Lecture 30 min including discussion<br />
Discussion Lecture 20 min including discussion<br />
6
Monday, March 18, 2013<br />
9.00 – 10.30 First morning session<br />
Chair: Ursula Biermann<br />
9.00 – 9.30 Metathesis: Commercialization <strong>of</strong> specialty chemicals from<br />
lipids (M)<br />
L5<br />
Mel Luetkens, Elevance Renewable Science, Woodridge , IL, USA<br />
9.30 – 9.50 News from the isomerizing alkoxycarbonylation (D)<br />
L6 Philipp Roesle 1 , Timo Witt 1 , Florian Stempfle 1 , Josefine T. Christl 1 ,<br />
Ilona Heckler 1 , Gerhard Müller 1 , Lucia Caporaso 2 , Stefan Mecking 1 ,<br />
1<br />
Department <strong>of</strong> Chemistry, University <strong>of</strong> Konstanz, Konstanz, Germany;<br />
2<br />
Department <strong>of</strong> Chemistry, University <strong>of</strong> Salerno, Fisciano (SA), Italy<br />
9.50 – 10.10 Polyesters and polyamides precursors from natural and waste<br />
oils (D)<br />
L7 Marc R. L. Furst 1 , David J. Cole-Hamilton 1 , Thomas Seidensticker 1 ,<br />
Ronan Le G<strong>of</strong>f 1 , Catherine H. Botting 1 , Dorothee Quinzler 2 , Stefan<br />
Mecking 2<br />
1 St. Andrews, Scotland, UK; 2 Department <strong>of</strong> Chemistry, University <strong>of</strong><br />
Konstanz, Konstanz, Germany<br />
10.10 – 10.30 Access to value-added products via metathesis <strong>of</strong> fats and terpene<br />
derivatives (D)<br />
L8<br />
Christian Bruneau, Cédric Fischmeister, Antoine Dupé, Hallouma Bilel,<br />
Université de Rennes 1, Sciences Chimiques, Rennes, France<br />
10.30 – 11.00 C<strong>of</strong>fee break<br />
7
11.00 – 12.50 Second morning session<br />
Chair: George John<br />
11.00 – 11.30 Fatty alcohols from triglycerides via catalytic hydrogenation (M)<br />
L9<br />
Dmitry G. Gusev, Denis Spasyuk, Wilfrid Laurier University, Waterloo,<br />
Ontario, Canada<br />
11.30 – 11.50 Fe-catalyzed oxidative cleavage <strong>of</strong> olefins towards aldehydes<br />
with hydrogen peroxide (M)<br />
L10<br />
Peter Spannring, Pieter C. Bruijnincx, Bert M. Weckhuysen, Bert Klein<br />
Gebbink, Utrecht University, Utrecht, Netherlands<br />
11.50 – 12.10 The first catalytic Lossen rearrangement: Sustainable access to<br />
fatty acid derived nitrogen containing monomers and polymers<br />
(D)<br />
L11<br />
Oliver Kreye, Sarah Wald, Maike Unverferth, Alexander Prohammer,<br />
Michael A. R. Meier, KIT, Karlsruhe, Germany<br />
12.10 – 12.30 Regioselective hydrogenation <strong>of</strong> vegetable oils with Pt/ZSM-5<br />
catalysts (D)<br />
L12<br />
An Philippaerts, Pierre Jacobs, Bert Sels, K.U.Leuven, Heverlee,<br />
Belgium<br />
12.30 – 12.50 Catalyst selection for conversion <strong>of</strong> fats and oils to renewable<br />
chemical products (D)<br />
L13<br />
Aalbert Zwijnenburg, Johnson Matthey Chemicals GmbH, Emmerich,<br />
Germany<br />
12.50 – 14.00 Lunch break<br />
8
14.00 – 15.30 First afternoon session<br />
Chair: Mel Luetkens<br />
14.00 – 14.30 ADM's Green Chemistry - platform chemicals based on<br />
renewable feedstock (M)<br />
L14<br />
Jürgen Fischer, Paul Bloom,<br />
ADM Research GmbH, Hamburg, Germany<br />
14.30 – 14.50 Isosorbide-based value products (D)<br />
L15<br />
Claudia Stoer, Markus Dierker, Claus Nieendick, Catherine Breffa,<br />
BASF Personal Care and Nutrition GmbH, Düsseldorf, Germany<br />
14.50 – 15.10 Polyurethane dispersions based on renewable resource materials<br />
– <strong>of</strong>f to pasture new! (D)<br />
L16<br />
Manfred Diedering, Markus Dimmers, Maria Ebert,<br />
Alberdingk Boley GmbH, Krefeld, Germany<br />
15.10 – 15.30 Development <strong>of</strong> transformer oils based on renewable raw<br />
materials (D)<br />
L17<br />
Günther Kraft, FUCHS Europe Schmierst<strong>of</strong>fe, Mannheim, Germany<br />
15.30 – 16.00 C<strong>of</strong>fee break<br />
9
16.00 – 17.30 Second afternoon session<br />
Chair: Dmitry G. Gusev<br />
16.00 – 16.30 Biorefinery: A sustainable design platform for green surfactants<br />
and s<strong>of</strong>t materials (M)<br />
L18<br />
George John, Department <strong>of</strong> Chemistry, The City College <strong>of</strong> the City<br />
University <strong>of</strong> New York, New York, USA<br />
16.30 – 16.50 Synthesis <strong>of</strong> fatty ethers: Catalytic reduction <strong>of</strong> fatty acid<br />
esters (D)<br />
L19<br />
Ursula Biermann, Jürgen O. Metzger, Universität Oldenburg and<br />
<strong>abiosus</strong> e.V., Oldenburg, Germany<br />
16.50 – 17.10 Additions to unsaturated fatty acid esters: Electrophilic<br />
additions via boron compounds and [2+2]-cycloadditions with<br />
N-chlorosulfonylethenimine to ß-lactams (D)<br />
L20<br />
Hans J. Schäfer, Theodor Lucas, Christian Kalk, Organischchemisches<br />
Institut der Universität Münster, Münster, Germany<br />
17.10 – 17.30 Singlet oxygenation <strong>of</strong> unsaturated monoglycerides in single-phase<br />
and multiphase systems using hydrogen peroxide catalyzed by<br />
molybdate anions (D)<br />
L21<br />
Hermine HNM NSA Moto, Zephirin MOULOUNGUI, Université de<br />
Toulouse, ENSIACET-INRA-INP Toulouse, Laboratoire de Chimie<br />
Agro-Industrielle, Toulouse, France<br />
19.30 Conference Dinner<br />
Renaissance Karlsruhe Hotel<br />
10
Tuesday, March 19, 2013<br />
9.00 – 10.40 First morning session<br />
Chair: Jürgen O. Metzger<br />
9.00 – 9.30 Synthesis <strong>of</strong> biobased building blocks from vegetable oils:<br />
towards platform chemicals (M)<br />
L22<br />
Sylvain Caillol, Remi Auvergne, Bernard Boutevin, ICGM - ENSCM,<br />
Montpellier, France<br />
9.30 – 10.00 Biobased polyamides past, present and future (M)<br />
L23<br />
Jürgen Herwig, Jasmin Nitsche, Harald Häger, Evonik, Marl,<br />
Germany<br />
10.00 – 10.20 Plant oil based renewable polyamide monomers and their<br />
polymers via efficient (catalytic) processes (D)<br />
L24<br />
Matthias Winkler, Oğuz Türünç, M. A. R. Meier, KIT, Karlsruhe,<br />
Germany<br />
10.20 – 10.40 Dimer fatty acids: Building blocks for a multitude <strong>of</strong> new<br />
macromolecular architectures (D)<br />
L25<br />
Luc Averous, ICPEES-ECPM University <strong>of</strong> Strasbourg, France<br />
10.40 – 11.10 C<strong>of</strong>fee break<br />
11
11.10 – 13.00 Second morning session<br />
Chair: Uwe Bornscheuer<br />
11.10 – 11.40 Enzyme-catalyzed reactions for fatty acids modification (M)<br />
L26<br />
Pierre Villeneuve, Erwann Durand, Jérôme Lecomte, Eric Dubreucq,<br />
UMR IATE, CIRAD, Montpellier, France<br />
11.40 – 12.00 Fine-tuning fatty acids length chain by metabolic engineering for<br />
“Single Cell Oils” strategies in Ashbya gossypii (D)<br />
L27<br />
Rodrigo Ledesma-Amaro, José Luis Revuelta, Universidad de<br />
Salamanca, Salamanca, Spain<br />
12.00 – 12.20 Bio-catalytic synthesis <strong>of</strong> small molecule oil structuring<br />
agents from renewable resources (D)<br />
L28<br />
Julian Silverman, George John, Department <strong>of</strong> Chemistry, The City<br />
College <strong>of</strong> New York, and The Graduate Center <strong>of</strong> The City<br />
University <strong>of</strong> New York, New York, New York<br />
12.20 – 12.40 Online analysis <strong>of</strong> polycondensations in a bubble column<br />
reactor using ATR-FTIR spectroscopy (D)<br />
L29<br />
Jakob Gebhard, Lutz Hilterhaus, Andreas Liese, Hamburg<br />
University <strong>of</strong> Technology, Hamburg, Germany<br />
12.40 – 13.00 Application <strong>of</strong> fatty acid chlorides in iron and zinc catalyzed<br />
depolymerization reactions (D)<br />
L30<br />
Stephan Enthaler, TU Berlin, Department <strong>of</strong> Chemistry, Cluster <strong>of</strong><br />
Excellence “Unifying Concepts in Catalysis”, Berlin, Germany<br />
13.00 – 14.00 Lunch break<br />
12
14.00 – 16.00 Afternoon session<br />
Chair: Sylvain Caillol<br />
14.00 – 14.20 Synthesis <strong>of</strong> Palm oil based ethylhexyl ester for drilling fluid<br />
application (D)<br />
L31<br />
Robiah Yunus, Nur Saiful Hafiz Habib, Zurina Zainal Abidin, Universiti<br />
Putra Malaysia, Selangor, Malaysia<br />
14.20 – 14.50 Biobased adhesives: when green chemistry meets the material<br />
science <strong>of</strong> sticky things (M)<br />
L32<br />
Richard Vendamme, Nitto Denko Corporation's European Research<br />
Committee (ERC), Nitto Europe NV, Belgium<br />
14.50 – 15.10 Microwave-assisted heterogeneous catalysis in esterification<br />
and etherification reactions (D)<br />
L33 Sabine Valange 1 , Gina Hincapie 2 , Diana Lopez 2 , Clement Allart 1 ,<br />
Joel Barrault 1 , 1 IC2MP, UMR CNRS 7285, ENSIP, Poitiers Cedex,<br />
France; 2 Institute <strong>of</strong> Chemistry, University <strong>of</strong> Antioquia, Medellin,<br />
Colombia<br />
15.10 – 15.30 Synthesis and application <strong>of</strong> cyclic carbonates <strong>of</strong> fatty acid<br />
esters (M)<br />
L34<br />
Benjamin Schäffner 1 , Matthias Blug 1 , Daniela Kruse 1 , Benjamin<br />
Woldt 1 , Mykola Polyakov 2 , Angela Köckritz 2 , Andreas Martin 2 ,<br />
Sebastian Jung 3 , David Agar 3 , Bettina Rüngeler 4 , Andreas Pfennig 5 ,<br />
Karsten Müller 5 , Wolfgang Arlt 5 , 1 Evonik Industries AG, Germany;<br />
2 Leibniz-Institute for Catalysis e.V., Rostock, Germany; 3 TU<br />
Dortmund, Dortmund, Germany; 4 RWTH Aachen, Aachen,<br />
Germany; 5 TU Graz, Graz, Austria; 6 University <strong>of</strong> Erlangen-<br />
Nuremberg, Erlangen, Germany<br />
15.30 Poster Award and Closing Remarks<br />
Best Poster Award<br />
Award committee: Bret J. Chisholm, Pierre Villeneuve, Richard<br />
Vendamme<br />
Closing remarks<br />
Michael A. R. Meier<br />
16.00 End <strong>of</strong> Workshop<br />
13
Posters<br />
P1<br />
P2<br />
P3<br />
P4<br />
P5<br />
P6<br />
P7<br />
P8<br />
P9<br />
P10<br />
Green synthesis <strong>of</strong> biolubricants from castor oil and higher chain alcohols<br />
Chandu S. Madankar, Subhalaxmi Pradhan, S.N. Naik, Indian Institute <strong>of</strong><br />
Technology, Delhi, India<br />
Potassium fluoride impregnated CaO/NiO: An efficient heterogeneous<br />
catalyst for transesterification <strong>of</strong> triglycerides<br />
Mandeep Kaur, Amjad Ali, Thapar University, Patiala India<br />
In-situ monitoring and induction time measurements during melt<br />
crystallization <strong>of</strong> plant based fatty acid mixtures in V-form reactor<br />
Sunanda Dasgupta, Peter Ay, Chair <strong>of</strong> Mineral Processing, Processing <strong>of</strong><br />
Biogenous Resources, Brandenburg University <strong>of</strong> Technology, Germany<br />
Biomass conversion: Preparation <strong>of</strong> glycerol carbonate esters by<br />
esterification with hybrid Nafion-silica catalyst<br />
Sergio Martínez Silvestre, Maria José Climent Olmedo, Avelino Corma Canós,<br />
Sara Iborra Chornet, Instituto de Tecnología Química, Valencia, Spain<br />
Time-resolved characterization <strong>of</strong> aging products from fatty acid methyl<br />
esters<br />
Stephanie Flitsch, Sigurd Schober, Martin Mittelbach, Institute <strong>of</strong> Chemistry,<br />
University <strong>of</strong> Graz; Graz, Austria<br />
Solvent Assisted Hydraulic Pressing <strong>of</strong> Dehulled Rubber Seeds<br />
Muhammad Yusuf Abduh, Erna Subroto, Robert Manurung, Hero Jan Heeres,<br />
Universitty <strong>of</strong> Groningen, Groningen, Netherlands<br />
Hydrotreating <strong>of</strong> Non-Food Fat and Oil Derivatives for the Production <strong>of</strong><br />
Bi<strong>of</strong>uels<br />
Alexander F. H. Studentschnig, Sigurd Schober, Martin Mittelbach, Institute <strong>of</strong><br />
organic/bioorganic Chemistry, Karl-Franzens University Graz, Graz,, Austria<br />
Enhancing the acyltransferase activity <strong>of</strong> Candida antarctica lipase A<br />
Janett Müller, Henrike Brundiek, Birte Fredrich, Uwe T. Bornscheuer, Univerity<br />
<strong>of</strong> greifswald, Greifswald, Germany<br />
Temperature and composition dependence <strong>of</strong> density for soybeanoil,<br />
epoxidized soybean oil and acetic acid binary mixtures<br />
Milovan Jankovic 1 , Olga Govedarica 1 , Snezana Sinadinovic-Fiser 1 , Vesna<br />
Rafajlovska 2<br />
1 Faculty <strong>of</strong> Technology, University <strong>of</strong> Novi Sad, Serbia; 2 Faculty <strong>of</strong> Technology<br />
and Metallurgy, SS Cyril and Methodious University in Skopje, Macedonia<br />
Renewable co-polymers derived from limonene and fatty acid derivatives<br />
Maulidan Firdaus, Michael A. R. Meier, Institute <strong>of</strong> Organic Chemistry,<br />
Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
14
P11<br />
P12<br />
P13<br />
P14<br />
P15<br />
P16<br />
P17<br />
P18<br />
Biphasic kinetic model <strong>of</strong> in situ epoxidation <strong>of</strong> castor oil with peracetic<br />
acid<br />
Milovan Jankovic, Snezana Sinadinovic-Fiser, Olga Govedarica, Faculty <strong>of</strong><br />
Technology, University <strong>of</strong> Novi Sad, Serbia<br />
Thiol-yne approach to biobased polyols: polyurethane synthesis and<br />
surface modification<br />
Cristina Lluch, Gerard Lligadas, Joan Carles Ronda, Marina Galià, Virginia<br />
Cádiz, Universitat Rovira i Virgili, Tarragona, Spain<br />
Heteropoly acids for conversion <strong>of</strong> renewable feedstocks<br />
Ali M. Alsalme, Abdulaziz A. Alghamdi, King Saud University, Riyadh, Saui-<br />
Arabia<br />
Flexible polyurethane foams modified with selectively hydrogenated<br />
Sylwia Dworakowska 1 , Dariusz Bogdal 1 , Federica Zaccheria 2 , Nicoletta<br />
Ravasio 2 ,<br />
1 Cracow University <strong>of</strong> Technology, Cracow, Poland; 2 Institute <strong>of</strong> Molecular<br />
Science and Technologies, National Research Council (CNR-ISTM), Milano,<br />
Italy<br />
Synthesis, purification and modification <strong>of</strong> abietic acid dimer, an<br />
interesting source <strong>of</strong> (co)monomers for the design <strong>of</strong> novel renewable<br />
polymers<br />
Audrey Llevot, Stephane Carlotti, Stephane Grelier, Henri Cramail,<br />
LCPO, PESSAC, France<br />
Rhodium-catalyzed hydr<strong>of</strong>ormylation <strong>of</strong> unsaturated fatty esters in<br />
aqueous media assisted by activated carbon<br />
Jérôme Boulanger, Frédéric Hapiot, Anne Ponchel, Eric Monflier,<br />
UCCS Artois, Lens, France<br />
Effect <strong>of</strong> some medicinal tea extracts on some oxidative parameters <strong>of</strong><br />
sesame oil<br />
Mehmet Musa Özcan 1 , Nurhan – Uslu 1 , Fahad Al Juhaimi 2 ,<br />
1 Selçuk University, Konya, Turkey; 2 King Saud University, Riyadh, Saui-Arabia<br />
Self-metathesis <strong>of</strong> fatty acid methyl esters: Full conversion by choosing<br />
the appropriate plant oil<br />
Robert H<strong>of</strong>säß, Hatice Mutlu, Rowena E. Montenegro, Michael A. R. Meier,<br />
Institute <strong>of</strong> Organic Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe,<br />
Germany<br />
P19 Synthesis and characterization <strong>of</strong> new biodegradable poly(linoleic acid) /<br />
poly(linolenic acid) graft copolymers<br />
Abdulkadir Allı 1 , Pınar Geçit 1 , Sema Allı 2 , Baki Hazer 2 ,<br />
1 Department <strong>of</strong> Chemistry, Düzce University, Düzce, Turkey; 2 Bülent Ecevit<br />
University, Turkey<br />
15
P20<br />
P21<br />
P22<br />
P23<br />
P24<br />
P25<br />
P26<br />
P27<br />
P28<br />
P29<br />
Diversity in ADMET monomer synthesis via Passerini three component<br />
reactions with 10-undecenal as key building block<br />
Ansgar Sehlinger, Lucas Montero de Espinosa, Michael A. R. Meier, Institute <strong>of</strong><br />
Organic Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
Malate production by Aspergillus orzyae<br />
Katrin Brzonkalik, Marina Bernhardt, Christoph Syldatk, Anke Neumann, KIT<br />
Technical Biology, Karlsruhe, Germany<br />
Monitoring <strong>of</strong> glyceride synthesis in multiphase system by ATR-Fourier<br />
transform infrared spectroscopy<br />
Sören Baum 1 , Martin Schilling 2 , Fabien Cabirol 2 , Lutz Hilterhaus 1 , Andreas<br />
Liese 1 ,<br />
Institute <strong>of</strong> Technical Biocatalysis, TH Hamburg, Hamburg, Germany; 2 Evonik<br />
Industries AG<br />
Pressure sensitive adhesives from renewable resources<br />
Wiebke Maassen, Norbert Willenbacher, Michael A. R. Meier, Institute <strong>of</strong><br />
Organic Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
Renewable aromatic aliphatic copolyesters derived from rapeseed<br />
Stefan Oelmann, Oliver Kreye, Michael A. R. Meier, Institute <strong>of</strong> Organic<br />
Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
Influence <strong>of</strong> the double bond configuration on the product composition <strong>of</strong><br />
Rh-catalyzed maleinisation <strong>of</strong> monounsaturated fatty acids<br />
Steven Eschig, Tunga Salthammer, Claudia Philipp, Fraunh<strong>of</strong>er Institute for<br />
Wood Research, Wilhelm-Klauditz-Institut, Braunschweig, Germany<br />
α-Arylation <strong>of</strong> saturated fatty acids: a sustainable approach to renewable<br />
monomers?<br />
Nicolai Kolb, Michael A. R. Meier, Institute <strong>of</strong> Organic Chemistry, Karlsruhe<br />
Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
New transfromations <strong>of</strong> ricinoleic acid derivatives<br />
Manuel Hartweg, Hatice Mutlu, Michael A. R. Meier, Institute <strong>of</strong> Organic<br />
Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
Self-metathesis derived renewable 1,4-cyclohexadiene and its potential<br />
applications<br />
Sarah Wald, Michael A. R. Meier, Institute <strong>of</strong> Organic Chemistry, Karlsruhe<br />
Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
Mesoporous niobium-silica materials for the epoxidation <strong>of</strong> vegetable oilderived<br />
mixtures <strong>of</strong> unsaturated fatty acid methyl esters (FAMEs)<br />
Cristina Tiozzo 1 , Nicoletta Ravasio 1 , Rinaldo Psaro 1 , Dariusz Bogdal 2 , Sylwia<br />
Dworakowska 2 , Matteo Guidotti 1 ,<br />
1 CNR-Institute <strong>of</strong> Molecular Sciences and Technologies, Milan, Italy; 2 Cracow<br />
University <strong>of</strong> Technology, Cracow, Poland<br />
16
P30<br />
P31<br />
P32<br />
Isomerizing ethenolysis <strong>of</strong> functionalized olefins<br />
Sabrina Baader, Dominik M. Ohlmann, Lukas J. Gooßen, Fachbereich Chemie,<br />
Organische Chemie, TU Kaiserslautern, Kaiserslautern, Germany<br />
Synthesis <strong>of</strong> oleic acid based-polymeric lattices through emulsion and<br />
miniemulsion polymerization<br />
Alan T. Jensen 1 , Claudia Sayer 2 , Pedro H. H. Araújo 2 , Fabricio Machado 1 ,<br />
1<br />
University <strong>of</strong> Brasilia, Brasilia, Brazil; 2 Federal University <strong>of</strong> Santa Catarina,<br />
Florianópolis – SC, Brazil<br />
Synthesis <strong>of</strong> polyurethane nanoparticles from renewable resources by<br />
miniemulsion polymerization<br />
Alexsandra Valerio 1 , Sandro R. P. da Rocha 2 , Claudia Sayer 1 , Pedro H. H.<br />
Araújo 1<br />
1 Federal University <strong>of</strong> Santa Catarina, Florianópolis – SC, Brazil; 2 Wayne<br />
State University<br />
17
<strong>Abstracts</strong><br />
Part 1: Lectures<br />
19
L1<br />
Polyurethanes from renewable resources and carbon dioxide<br />
Rolf Mülhaupt<br />
Freiburg Materials Research Center and Institute for Macromolecular Chemistry,<br />
Freiburg, Germany<br />
rolf.muelhaupt@makro.uni-freiburg.de<br />
Since the pioneering advances by Otto Bayer, polyurethanes are well recognized as very<br />
versatile class <strong>of</strong> materials, which can be tailored to meet the demands <strong>of</strong> highly diversified<br />
applications, ranging from low weight engineering plastics to elastomers, fibers, foams,<br />
coatings and adhesives. The quest for green economy and growing concerns regarding<br />
global warming are stimulating the development <strong>of</strong> biobased polyurethanes and<br />
polyurethanes derived from the greenhouse gas carbon dioxide. Traditionally, renewable<br />
resources play an important role in polyurethane technology, particularly in manufacturing<br />
<strong>of</strong> polyols and prepolymers. For example, polyols are produced by propoxylation <strong>of</strong> various<br />
sugars and natural oils such as soybean and castor oil. Owing to progress in propoxylation<br />
chemistry, odor and color problems, have been eliminated, improving properties <strong>of</strong> such<br />
biobased polyurethanes. A variety <strong>of</strong> biobased polyols are commercially available. New<br />
routes are developed to produce propyleneoxide from glycerol, which is a byproduct <strong>of</strong> the<br />
biodiesel production. Intermediates <strong>of</strong> biorefineries are attractive components for making<br />
polyurethanes. Instead <strong>of</strong> using biocatalytic carbon dioxide conversion and biomass, new<br />
processes employ the direct chemical fixation <strong>of</strong> carbon dioxide. For instance,<br />
copolymerization <strong>of</strong> propylene oxide with carbon dioxide affords polypropylenecarbonates<br />
as new polyols for polyurethanes. In green polyurethane chemistry the use <strong>of</strong> isocyanates<br />
is eliminated. Key intermediates are cyclic carbonates, prepared by reacting polyepoxides<br />
with carbon dioxide, which are cured with amines. Both epoxidized unsaturated natural oils<br />
and epoxidized terpenes are used as raw materials, aiming at preventing competition with<br />
food production. This presentation will give an overview on trends and prospects <strong>of</strong><br />
biobased polyurethanes, focusing on the direct conversion <strong>of</strong> carbon dioxide and the<br />
prospects <strong>of</strong> green polyurethanes.<br />
20
L2<br />
Novel high molecular weight vinyl ether polymers based on plant oils<br />
Samim Alam, Harjyoti Kalita, Satyabrata Samanta, Andrey Chernykh, Bret J. Chisholm,<br />
North Dakota State University, Fargo (ND), USA<br />
bret.chisholm@ndsu.edu<br />
A platform technology that has been developed that involves the production <strong>of</strong> a vinyl ether<br />
monomer using simple base-catalyzed transesterification <strong>of</strong> a plant oil triglyceride with a<br />
hydroxy-functional vinyl, ether such as 4-(vinyloxy)butanol or 2-(vinyloxy)ethanol, to<br />
produce a mixture <strong>of</strong> vinyl ether monomers that possess fatty acid ester groups in their<br />
structure. This process is essentially the same as that used to produce biodiesel (i.e.<br />
methylesters <strong>of</strong> plant oil fatty acids) with the exception that the hydroxy-functional vinyl<br />
ether is used in place <strong>of</strong> methanol. A key aspect <strong>of</strong> the technology involves the<br />
polymerization process that allows for high molecular weight polymers to be produced by<br />
polymerization exclusively through the vinyl ether double bonds. This feature enables<br />
polymers to be produced that possess unsaturation in the fatty acid ester pendent groups<br />
derived from the plant oil starting material. As has been done for conventional plant oil<br />
triglycerides, the double bonds can be used to produce thermoset materials either directly<br />
through an oxidative process or by derivatization to produce other functional groups, such<br />
as epoxides, acrylates, and hydroxyls, that can be subsequently used to produce<br />
crosslinked networks. The polymerization process also results in a “living” polymerization<br />
that allows for control <strong>of</strong> polymer molecular weight, narrow molecular weight distributions,<br />
and the production <strong>of</strong> unique polymer architectures such as block copolymers and multiarm<br />
star polymers. Another very important feature <strong>of</strong> the technology involves the ability to<br />
copolymerize the plant oil-based vinyl ether monomers with other monomers to tailor<br />
polymer properties such as glass transition temperature, mechanical properties, and<br />
solubility/compatibility with other materials.<br />
21
L3<br />
Protein engineering and application <strong>of</strong> enzymes in lipid modification<br />
Uwe T. Bornscheuer<br />
Institute <strong>of</strong> Biochemistry, Greifswald University, Germany<br />
bornsche@uni-greifswald.de<br />
Protein engineering has developed in the past decade to an important technology to alter<br />
the properties <strong>of</strong> enzymes [1-3]. Whereas initially rational protein design was the method<br />
<strong>of</strong> choice, directed evolution (in essence a random mutagenesis followed by screening or<br />
selection <strong>of</strong> desired mutants) became an important alternative. More recently, researchers<br />
used combinations <strong>of</strong> both methods. We applied extensive protein engineering guided by<br />
advanced bioinformatic tools in combination with high-throughput screening to alter the<br />
fatty acid selectivity <strong>of</strong> lipase A from Candida antarctica (CAL-A). This resulted in the<br />
creation <strong>of</strong> mutants with excellent selectivity for trans- and saturated fatty acids in the<br />
hydrolysis <strong>of</strong> partially hydrogenated plant oil [4]. Hence, this lipase variant now enables to<br />
substantially reduce the trans-fatty acid content providing access to healthy oil for human<br />
nutrition. Furthermore, we identified by sequence comparison a lipase from Ustilago<br />
maydis, which also shows trans-fatty acid selectivity [5]. Another mutant <strong>of</strong> CAL-A was<br />
found to show distinct selectivity for medium chain fatty acids [6]. We also developed a<br />
process to reduce the monoglyceride content in commercial biodiesel by applying a<br />
monoglyceride-selective lipase from Penicillium camembertii [7].<br />
[1] Kazlauskas, R.J., Bornscheuer, U.T. (2009) Nature Chem. Biol., 5, 526-529<br />
[2] Bornscheuer, U.T., Huisman, G., Kazlauskas, R.J., Lutz, S., Moore, J., Robins, K.<br />
(2012), Nature, 485, 185-194.<br />
[3] Kourist, R., Brundiek, H., Bornscheuer, U.T. (2010) Eur. J. Lipid Sci. Technol., 112, 64-<br />
74,<br />
[4] Brundiek, H.B., Evitt, A.S., Kourist, R., Bornscheuer, U.T. (2012) Angew. Chem. Int.<br />
Ed., 51, 412-414.<br />
[5] Brundiek, H., Sass, S., Evitt, A., Kourist, R., Bornscheuer, U.T. (2012), Appl. Microb.<br />
Biotechnol., online; DOI: 10.1007/s00253-012-3903-9.<br />
[6] Brundiek, H., Padhi, S.K., Evitt, A., Kourist, R., Bornscheuer, U.T (2012), Eur. J. Lipid<br />
Sci. Technol., 114, 1148-1153.<br />
[7] Padhi, S.K., Haas, M., Bornscheuer, U.T. (2012), Eur. J. Lipid Sci. Technol., 114, 875-<br />
879.<br />
22
L4<br />
Epicerol ® and the environmental challenges <strong>of</strong> bio-based chemistry<br />
Thibaud Caulier, Solvay, Brussels, Belgium<br />
thibaud.caulier@solvay.com<br />
The use <strong>of</strong> more renewable resources is an important trend in the chemical industry. This<br />
evolution is well illustrated by Epicerol®, the Solvay patented process to manufacture biobased<br />
epichlorohydrin (ECH) from natural glycerin.<br />
To better understand the environmental footprint <strong>of</strong> this technology, we performed a life<br />
cycle assessment benchmarking Epicerol® with the traditional propylene-based ECH<br />
manufacturing process. This comparative eco-footprint shows that, for the same quantity<br />
<strong>of</strong> ECH produced, Epicerol®:<br />
- reduces the non renewable energy demand and the impact on climate change;<br />
- has a detrimental impact on the quantitative land use and the eco-toxicity;<br />
- does not significantly modify the water consumption.<br />
The Epicerol® process allows the chemical industry to reduce its direct environmental<br />
footprint (from gate to gate) thanks to an optimization <strong>of</strong> the resources (less consumption<br />
<strong>of</strong> energy, chlorine and water), and a reduction <strong>of</strong> the emissions (CO2, chlorides and water<br />
effluents) and by-product formation (chlorinated organics).<br />
From cradle to gate, the use <strong>of</strong> renewable glycerin reinforces the Epicerol® gate to gate<br />
advantages on non renewable energy consumption and CO2 balance (thanks to the<br />
biogenic carbon capture). Paradoxically, renewable glycerin also contributes to a<br />
degradation <strong>of</strong> other environmental parameters. It is true not only for the quantitative land<br />
use (impact <strong>of</strong> farmlands) and the eco-toxicity (impact <strong>of</strong> plant protection products<br />
released in the environment), but also for the water consumption (impact <strong>of</strong> irrigation)<br />
which appears neutral from cradle to gate despite the fact that Epicerol® saves a lot <strong>of</strong><br />
process water from gate to gate.<br />
The Epicerol® sustainability issues inherited from the agriculture are fundamentally<br />
different from the sustainability issues faced by the petrochemical route. They are usually<br />
managed by the agro-companies who face pressure in their mainstream food businesses<br />
and by the biodiesel industry where authorities are progressively setting strict sustainability<br />
criteria.<br />
A lot <strong>of</strong> improvements are still to be expected in the production <strong>of</strong> glycerin. They are in the<br />
crop yield, in the water consumption and in the general farming operations. The bio-based<br />
chemical industry can contribute to this evolution, by the development <strong>of</strong> sustainable<br />
sourcing policies involving a close collaboration with raw material suppliers.<br />
23
L5<br />
Metathesis: Commercialization <strong>of</strong> Specialty Chemicals From Lipids<br />
Mel Luetkens, Elevance Renewable Science, Woodridge , IL, USA<br />
Mel.Luetkens@elevance.com<br />
Elevance produces high-performance, cost-advantaged green chemicals from renewable<br />
oils. Its process uses Nobel Prize-winning innovations in metathesis catalysis, consumes<br />
significantly less energy and reduces greenhouse gas (GHG) emissions compared to<br />
petrochemical technologies. The process use a highly efficient, selective catalyst to<br />
produce olefins and novel fatty ester fragments from natural oils. The core process<br />
technology is based on the work <strong>of</strong> Nobel Laureate Dr. Robert H. Grubbs. In 2011,<br />
Elevance expanded its proprietary technology in metathesis with a licensing agreement<br />
with XiMo AG to use proprietary molybdenum and tungsten metathesis catalysts based on<br />
the work <strong>of</strong> Nobel Laureate Dr. Richard Schrock.<br />
The resulting products from its biorefinery are high-value, difunctional chemicals with<br />
superior functional attributes previously unavailable commercially. These molecules<br />
combine the functional attributes <strong>of</strong> an olefin, typical <strong>of</strong> petrochemicals, and a<br />
mon<strong>of</strong>unctional ester or acid, typical <strong>of</strong> biobased oleochemicals, into a single molecule.<br />
Conventional producers have to blend petrochemicals and biobased oleochemicals in<br />
attempts to achieve these functional attributes simultaneously, which when possible,<br />
increase their production costs. Elevance’s difunctional building blocks change this<br />
paradigm by creating specialty chemical molecules which simultaneously include desired<br />
attributes enabled by both chemical families<br />
Elevance’s products enable novel surfactants, lubricants, additives, polymers, and<br />
engineered thermoplastics. Elevance has completed validation <strong>of</strong> its several processes in<br />
toll manufacturing and it is completing its world-scale biorefinery in Gresik, Indonesia.<br />
Elevance has also secured strategic partnerships with value chain global leaders to<br />
accelerate deployment and commercialization for these products. In this presentation, the<br />
biorefinery process, the biorefinery products, and some markets for the products will be<br />
discussed.<br />
24
L6<br />
News from the isomerizing alkoxycarbonylation<br />
Philipp Roesle 1 , Timo Witt 1 , Florian Stempfle 1 , Josefine T. Christl 1 , Ilona Heckler 1 ,<br />
Gerhard Müller 1 , Lucia Caporaso 2 , Stefan Mecking 1 ,<br />
1<br />
Department <strong>of</strong> Chemistry, University <strong>of</strong> Konstanz, Konstanz, Germany;<br />
2 Department <strong>of</strong> Chemistry, University <strong>of</strong> Salerno, Fisciano (SA), Italy<br />
Philipp.Roesle@uni-konstanz.de<br />
Thermoplastic polymers are currently prepared almost exclusively from fossil feedstocks. In view <strong>of</strong><br />
the limited availability <strong>of</strong> such feedstocks, alternative renewable resources are desirable in the long<br />
term. 1 Due to their unique long methylene sequences, fatty acid esters from plant oils are attractive<br />
substrates for monomer generation. 2 By means <strong>of</strong> isomerizing alkoxycarbonylation such<br />
unsaturated fatty acids are converted into long-chain linear diesters in polycondensation grade<br />
purity (> 99 %). 3a,3b These diesters are the basis for novel polycondensation monomers such as<br />
long-chain diols or diamines, as well as for novel polycondensates such as aliphatic polyesters and<br />
polyamides with melting and crystallization points suitable for thermoplastic processing. 3b,3c<br />
In the discussion lecture we want to present an overview <strong>of</strong> our current research activities in the<br />
field <strong>of</strong> the isomerizing alkoxycarbonylation <strong>of</strong> fatty acid esters: a full mechanistic study <strong>of</strong> this<br />
unusual, highly selective reaction, by direct observation <strong>of</strong> the relevant intermediates with NMR<br />
spectroscopic methods, supported by DFT calculations and X-ray structure analysis (identification<br />
<strong>of</strong> the intermediates was performed by various NMR spectroscopic methods assisted by the use <strong>of</strong><br />
13C enriched compounds). 4 Moreover, structure-activity relationship <strong>of</strong> the diphosphine Pd(II)<br />
catalysts, as well as the scope and limitations <strong>of</strong> this reaction will be discussed.<br />
[1] a) D. R. Dodds, R. A. Gross, Science 2007, 318, 1250 - 1251. b) S. Mecking, Angew. Chem. Int. Ed.<br />
2004, 43, 1078 - 1085. c) M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788 -<br />
1802. d) U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O. Metzger, H. J. Schäfer, Angew. Chem. Int. Ed.<br />
2011, 50, 3854 - 3871.<br />
[2] a) U. Biermann, W. Friedt, S. Lang, W. Lühs, G. Machmüller, J. O. Metzger, M. Rüsch-Klaas, H. J.<br />
Schäfer, and M. P. Schneider, Angew. Chem Int. Ed. 2000, 39, 2206 - 2224. b) C. Vilela, A. J. D. Silvestre,<br />
M. A. R. Meier, Macromol. Chem. Phys. 2012, 213, 2220 - 2227. c) F. Stempfle, P. Ortmann, S. Mecking,<br />
Macromol. Rapid Commun. 2013, 34, 47 - 50.<br />
[3] a) C. Jiménez-Rodriguez, G. R. Eastham, D. J. Cole-Hamilton, Inorg. Chem. Commun. 2005, 8, 878 -<br />
881. b) D. Quinzler, S. Mecking, Angew. Chem. Int. Ed. 2010, 49, 4306 - 4308. c) F. Stempfle, D. Quinzler, I.<br />
Heckler, S. Mecking, Macromolecules 2011, 44, 4159 - 4166.<br />
[4] P. Roesle, C. J. Dürr, H. M. Möller, L. Cavallo, L. Caporaso, S. Mecking, J. Am. Chem. Soc. 2012, 134,<br />
17696 - 17703.<br />
25
L7<br />
Polyesters and polyamides precursors from natural and waste oils<br />
Marc R. L. Furst 1 , David J. Cole-Hamilton 1 , Thomas Seidensticker 1 , Ronan Le G<strong>of</strong>f 1 ,<br />
Catherine H. Botting 1 , Dorothee Quinzler 2 , Stefan Mecking 2<br />
1 St. Andrews, Scotland, UK ; 2 Department <strong>of</strong> Chemistry, University <strong>of</strong> Konstanz, Konstanz,<br />
Germany<br />
mrlf2@st-andrews.ac.uk<br />
As oil feedstocks dwindle, there will be a need for alternative feedstocks to produce the<br />
many chemicals that so enhance our lives. The search for renewable raw materials from<br />
agricultural resources, which can be synthesised into environmentally friendly low cost<br />
polymers, is a burgeoning area.<br />
We describe the production <strong>of</strong> different monomers for the production <strong>of</strong> polyesters and<br />
polyamides. Dimethyl 1,19-nonadecanedioate is obtained from the methoxycarbonylation<br />
<strong>of</strong> commercial olive, rapeseed or sunflower oils in the presence <strong>of</strong> a catalyst derived from<br />
[Pd2(dba)3], bis(ditertiarybutylphosphinomethyl)benzene and methane sulphonic acid. The<br />
diester is then easily hydrogenated to 1,19-nonadecanediol using Ru/1,1,1-tris-<br />
(diphenylphosphinomethyl)ethane in aqueous media. The corresponding carboxylic acid is<br />
easily obtained by a simple acid hydrolysis, which leads to short chain oligoesters by<br />
anhydrous hydrogenation, which can themselves be hydrogenated to 1,19-nonadecanol by<br />
hydrogenation in the presence <strong>of</strong> water.<br />
One <strong>of</strong> the key aspirations <strong>of</strong> Green Chemistry is to produce useful chemicals from<br />
renewable resources, but it is also important to use feedstocks which are available as side<br />
products from other processes so that the Chemical syntheses does not require land<br />
which could be used for food production.<br />
Dimethyl 1,19-nonadecanedioate can thenbe obtained from Tall Oil fatty Acids (TOFA), a<br />
side product from paper manufacture from pine trees using the Kraft process.<br />
Moreover, we show that methoxycarbonylation <strong>of</strong> TOFA can give isomeric triesters,<br />
trimethyl 1,n,17-heptadecanetricarboxylate, which are isolated in moderate yield from<br />
methoxycarbonylation <strong>of</strong> linoleic acid. The methoxycarbonylation <strong>of</strong> methyl linoleate is<br />
used to gain understanding <strong>of</strong> the products obtained from TOFA and to optimise that<br />
reaction.<br />
Moreover, a derivative from castor oil, methyl undecen-10-enoate, is aminocarboxylated<br />
into methyl 12-oxo-12-(phenylamino)dodecanoate, in the presence <strong>of</strong> aniline and the<br />
previously described palladium catalyst.<br />
26
L8<br />
Access to value-added products via metathesis <strong>of</strong> fats and terpene<br />
derivatives<br />
Christian Bruneau, Cédric Fischmeister, Antoine Dupé, Hallouma Bilel,<br />
UMR 6226 CNRS-Université de Rennes 1, Institut Sciences Chimiques de Rennes,<br />
Organométallique : Matériaux et Catalyse, Rennes cedex. France<br />
christian.bruneau@univ-rennes1.fr<br />
Plant oils and terpene derivatives constitute a class <strong>of</strong> renewable raw materials, which can<br />
produce a large variety <strong>of</strong> chemicals useful for polymer and fine chemical industry.<br />
We will show that cross-metathesis <strong>of</strong> terpenoids produces in one step new functionalized<br />
terpene derivatives upon reaction with acrylic derivatives. [1]<br />
O<br />
O<br />
+<br />
O<br />
Ru cat.<br />
(Scheme 1)<br />
MeO<br />
CO 2 Me<br />
The alcohol functionality <strong>of</strong> methyl ricinoleate provides a convenient entry to the<br />
preparation <strong>of</strong> dienes. The ring closing metathesis reaction concomitently leads to<br />
dihydropyrans derivatives, which are potentially useful for flavor and flagrance<br />
applications, and methyl 9-decenoate and dimethyl octa-9-decenoate (its self-metathesis<br />
product), which are polymer precursors (Scheme 2). [2]<br />
R 2 R 1<br />
OH<br />
O<br />
MeO 2<br />
C<br />
7<br />
5<br />
MeO 2 C<br />
7<br />
Ru catalyst<br />
5<br />
7<br />
CO 2 Me<br />
R 1<br />
R 2<br />
O<br />
Scheme 2<br />
MeO 2 C<br />
MeO 2 C<br />
7 7<br />
5<br />
_______________<br />
[1] H. Bilel, N. Hamdi, F. Zagrouba, C. Fischmeister, C. Bruneau, Green Chem.,<br />
2011, 13, 1448.<br />
[2] A. Dupé, M. Achard, C. Fischmeister, C. Bruneau, ChemSusChem, 2012, 5, 2249.<br />
27
L9<br />
Fatty alcohols from triglycerides via catalytic hydrogenation<br />
Dmitry G. Gusev, Denis Spasyuk, Wilfrid Laurier University, Waterloo, Ontario, Canada<br />
dgoussev@hotmail.com<br />
Reduction <strong>of</strong> carboxylic esters is typically accomplished with the help <strong>of</strong> aluminum<br />
hydrides. This approach is hazardous and has a challenging work-up protocol due to the<br />
highly exothermic hydrolysis step yielding voluminous precipitates. An attractive 'green'<br />
alternative to the classical method is the catalytic hydrogenation: RCOOR' + 2H2 -><br />
RCH2OH + R'OH, and there has been much recent academic and industrial interest in<br />
reduction <strong>of</strong> esters under hydrogen gas. This presentation concerns the results <strong>of</strong> catalytic<br />
research in our group. In the last two years, we succeeded in developing a series <strong>of</strong> ester<br />
hydrogenation catalysts distinguished by low costs <strong>of</strong> production, high efficiency, and<br />
currently best selectivity for the reduction <strong>of</strong> unsaturated esters. Examples <strong>of</strong> applications<br />
<strong>of</strong> the catalytic hydrogenation for reduction <strong>of</strong> esters <strong>of</strong> fatty acids, triglycerides and natural<br />
oils will be presented. The mechanistic details <strong>of</strong> the chemical process, practical<br />
challenges, and perspectives <strong>of</strong> the catalytic approach for conversion <strong>of</strong> fats and oils into<br />
fatty alcohols will be discussed.<br />
28
L10<br />
Fe-catalyzed oxidative cleavage <strong>of</strong> olefins towards aldehydes with<br />
hydrogen peroxide<br />
Peter Spannring, Pieter C. Bruijnincx, Bert M. Weckhuysen, Bert Klein Gebbink,<br />
Utrecht University, Utrecht, Netherlands<br />
r.j.m.kleingebbink@uu.nl<br />
Olefins can be found in nature as terpenes or unsaturated fatty acids, which are derived<br />
from vegetable oils and animal fats. Oxidative cleavage <strong>of</strong> these bio-based alkenes yields<br />
mono- or dicarbonyl compounds, i.e. aldehydes or carboxylic acids, which can be used in<br />
polymer, plasticizer and stabilizer production. These compounds are also useful as<br />
intermediate building blocks for subsequent reactions.<br />
Industrially, the oxidative cleavage <strong>of</strong> oleic acid is done by ozonolysis, yet this oxidant is<br />
hazardous. Expensive and <strong>of</strong>ten toxic transition-metal complexes derived from Ru [1], W<br />
[2] or Os [3] are known to catalyze these specific oxidative cleavages, with the help <strong>of</strong><br />
reactive and relatively hazardous oxidants like NaIO4 or oxone. On the other hand, firstrow<br />
transition-metal complexes are primarily known to cleave styrene-derivatives into<br />
benzaldehyde [4]. Permanganate may also be used for these reactions, yet it has to be<br />
used in stoichiometric amounts.<br />
Here, we present a study towards the use <strong>of</strong> more benign methods to oxidatively cleave<br />
aliphatic double bonds and unsaturated fatty acids into aldehydes, using Fe-catalysts and<br />
hydrogen peroxide. Ultimately, such procedures can be seen as green alternatives for the<br />
production <strong>of</strong> chemical building blocks from renewable sources.<br />
[1] Rup, S., Zimmermann, F., Meux, E., Schneider, M., Sindt, M. and Oget, N., Ultras.<br />
Sonoch. 16 (2009) 266.<br />
[2] Turnwald, S.E., Lorier, M.A., Wright, L.J. and Mucalo M.R., J. Mat. Sci. Lett. 17 (1998)<br />
1305.<br />
[3] Ley, S.V., Ramarao, C., Lee, A.L., Oostergaard, N., Smith, S.C. and Shirley, I.M., Org.<br />
Lett. 5 (2003) 185.<br />
[4] Dhakshinamoorthy, A. and Pitchumani, K., Tetrah. 62 (2006) 9911.<br />
29
L11<br />
The first catalytic Lossen rearrangement: Sustainable access to fatty<br />
acid derived nitrogen containing monomers and polymers<br />
Oliver Kreye, Sarah Wald, Maike Unverferth, Alexander Prohammer, Michael A. R. Meier,<br />
KIT, Karlsruhe, Germany<br />
oliver.kreye@kit.edu<br />
A new highly efficient and environmentally benign catalytic variant <strong>of</strong> the Lossen<br />
rearrangement is described.[1] Dimethyl carbonate (DMC) as green activation reagent <strong>of</strong><br />
hydroxamic acids in presence <strong>of</strong> catalytic amounts <strong>of</strong> tertiary amine bases (TBD, DBU,<br />
DABCO and triethylamine) and small quantities <strong>of</strong> methanol initiate the rearrangement.[2]<br />
Methyl carbamates were obtained in good to moderate yields if aliphatic hydroxamic acids<br />
were employed in this catalytic Lossen rearrangement; under the same conditions<br />
aromatic hydroxamic acids yielded anilines. Notably, the mixture <strong>of</strong> DMC / methanol was<br />
recycled several times without observing decreased yields, thus minimizing the produced<br />
waste. Moreover, several other organic carbonates (e.g. bis-allyl- or bis-benzyl-carbonate)<br />
were successfully employed in the introduced catalytic Lossen rearrangement procedure.<br />
The rearrangements <strong>of</strong> fatty acid derived dihydroxamic acids afforded a facile and<br />
sustainable entry to valuable dimethyl carbamate monomers for the synthesis <strong>of</strong> nonisocyanate<br />
polyurethanes (NIPUs).[3] The conversion <strong>of</strong> these monomers with different<br />
aliphatic diols gave structurally diverse thermoplastic NIPUs with molecular weights up to<br />
17 kDa after intensive optimizations regarding the used catalytic system and reaction<br />
conditions.<br />
[1] H. L. Yale, Chem. Rev. 1943, 33, 209; L. Bauer, O. Exner, Angew. Chem. Int. Ed.<br />
1974, 13, 376.<br />
[2] O. Kreye, S. Wald, M. A. R. Meier, Adv. Synth. Catal. 2013, DOI:<br />
10.1002/adsc.201200760.<br />
[3] O. Kreye, M. Unverferth, A. Prohammer, M. A. R. Meier, Manuscript in preparation.<br />
30
L12<br />
Regioselective hydrogenation <strong>of</strong> vegetable oils with Pt/ZSM-5 catalysts<br />
An Philippaerts, Pierre Jacobs, Bert Sels, K.U.Leuven, Heverlee, Belgium<br />
an.philippaerts@biw.kuleuven.be<br />
Catalytic hydrogenation <strong>of</strong> vegetable oils is a well-known process in food industry to make<br />
the oil more resistant against air autoxidation and/or to obtain fats with a certain melting<br />
pr<strong>of</strong>ile.[1] With the increasing interest <strong>of</strong> vegetable oils as a renewable feedstock, the<br />
selective hydrogenation <strong>of</strong> triglyceride molecules is also important for industrial<br />
applications, as for instance in the production <strong>of</strong> bio-lubricants.[2]<br />
Importantly, the competitive isomerization leading to trans fatty acids needs to be<br />
eliminated as much as possible both in food as industrial applications as they are<br />
considered a risk factor in coronary heart diseases[3] and/or have a too high melting point,<br />
respectively. Unfortunately, literature learns that low cis/trans isomerization is almost<br />
always associated with a lower hydrogenation selectivity, implying that the unstable<br />
polyunsaturated fatty acids are not selectively converted to the more stable monounsaturates.[4]<br />
In this contribution, a new catalytic concept with shape-selective Pt/ZSM-5 catalysts, that<br />
is able to decouple the isomerization/hydrogenation selectivity, will be presented.[5]<br />
Chemical and physical analysis <strong>of</strong> the new fat products against commercial benchmarks<br />
will be given to show its ideal physical properties despite its essentially trans-free<br />
composition.[6]<br />
It will be shown that the improved selectivity obtained with the Pt/ZSM-5 catalyst results<br />
from a unique regioselectivity in which the fatty acids located on the central position (sn-2)<br />
are preferentially hydrogenated. As vegetable oils contain their polyunsaturated fatty acids<br />
mostly at the central position <strong>of</strong> the triglyceride molecules, these will be preferentially<br />
hydrogenated and hence stabilized without significant trans fatty acid formation.<br />
Experiments with Pt/ZSM-5 catalysts with different crystal sizes prove that this<br />
unprecedented regioselective property is a consequence <strong>of</strong> pore-mouth catalysis, in which<br />
only one fatty acid chain is able to enter the small micropores <strong>of</strong> the ZSM-5 zeolite where it<br />
will be hydrogenated by the internal Pt nanoclusters.<br />
[1] H.B.W. Patterson in “Hydrogenation <strong>of</strong> Fats and Oils: Theory and Practice, AOCS<br />
press, 1994.<br />
[2] a) N. Ravasio, F. Zaccheria, M. Cargano, S. Recchia, A. Fusi, N. Poli, R. Psaro, Appl.<br />
Catal. A 2002, 233, 1-6; b) U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O. Metzger, H.<br />
J. Schäfer, Angew. Chem. Int. Ed. 2011, 50, 3854-3871; Angew. Chem. 2011, 123, 3938-<br />
3956.<br />
[3] D. Mozaffarian, M. Katan, A. Ascherio, M. Stampfer, Willett, W. N. Engl. J. Med. 2006,<br />
354, 1601-1613.<br />
[4] A. Philippaerts, P.A. Jacobs, B.F. Sels, Angew. Chem. Int. Ed. (accepted)<br />
[5] A. Philippaerts, S. Paulussen, A. Beersch, S. Turner, O.I. Lebedev, G. Van Tendeloo,<br />
B. Sels, P. Jacobs, Angew. Chem. Int. Ed. 2011, 50, 3947-3949; Angew. Chem. 2011,<br />
123, 4033-4035.<br />
[6] A. Philippaerts, A. Breesch, G. De Cremer, P. Kayaert, J. H<strong>of</strong>kens, G. Van den Mooter,<br />
P. Jacobs, B. Sels, J. Am. Oil Chem. Soc. 2011, 88, 2023-2034.<br />
31
L13<br />
Catalyst selection for conversion <strong>of</strong> fats and oils to renewable chemical<br />
products<br />
Aalbert Zwijnenburg, Johnson Matthey Chemicals GmbH, Emmerich, Germany<br />
bart.zwijnenburg@matthey.com<br />
This contribution will focus on how to select optimal catalysts for the conversion <strong>of</strong> fats and<br />
oils to renewable chemical products. To achieve commercially attractive products, in<br />
general, fats and oils need oxygen removal and or hydrogen addition.<br />
These reactions are best carried out via metallic catalysts. The presentation will focus on<br />
how to select most promising catalysts, by following design rules on the feedstock acidity,<br />
the expected scale <strong>of</strong> the production plant and the expected purity <strong>of</strong> the starting material.<br />
By synthetic biology, new feedstocks are becoming available, such as terpenes and fatty<br />
alcohols. These new material potentially need less chemical conversion (such as oxygen<br />
removal and/or hydrogen addition). It will be shown how these feedstocks differ from the<br />
traditional raw materials and how this affects the catalysis. Also the applicability <strong>of</strong> the<br />
general catalyst selection rules will be discussed.<br />
To illustrate the catalyst selection process, an overview <strong>of</strong> traditional fatty alcohol<br />
developments will be given and this will be linked to most recent developments in this<br />
area.<br />
32
L14<br />
ADM’s Green Chemistry – Platform Chemicals Based on Renewable<br />
Feedstock<br />
Jürgen Fischer, Paul Bloom, ADM Research GmbH, Hamburg, Germany<br />
Juergen.Fischer@adm.com<br />
Archer Daniels Midland, founded in 1902 as a linseed crushing plant, is today one <strong>of</strong> the<br />
world’s largest agricultural companies, with its activities covering the whole value chain.<br />
The development <strong>of</strong> new technologies and products is indispensable to make the company<br />
fit for the future and to assure its position in the world.<br />
The technical use <strong>of</strong> bio-based products has a long history. Today, ADM’s industrial<br />
products cover a wide range comprising bi<strong>of</strong>uels, sugars and specialty chemicals amongst<br />
others solvents.<br />
Worldwide research on chemicals from biomass focuses on two major pathways:<br />
1. Direct replacement <strong>of</strong> existing substances by their “bio” versions<br />
Direct replacement is the preferred option since products and intermediates from<br />
conventional production routes can be replaced by their identical biobased version. Good<br />
examples are propylene glycol (PG), ethylene glycol (EG) and acrylic acid. PG and EG<br />
can easily be produced from biomass by hydrogenolysis <strong>of</strong> glycerol and sugars. This<br />
reaction with hydrogen under mild conditions is a direct replacement for the production<br />
from fossil resources. ADM’s propylene glycol plant has been in operation since 2010,<br />
producing high quality PG with significantly lower CO2 emissions compared to the<br />
petrochemical route. Propylene glycol is used as a key component i.e. in resins,<br />
cosmetics, detergents and deicers. Acrylic Acid is a common platform chemical for many<br />
applications. ADM is currently piloting a plant for the conversion <strong>of</strong> biomass to ethanol and<br />
acrylic acid/esters.<br />
2. Bioadvantaged molecules: new intermediates from biomass able to replace existing<br />
ones from fossil sources.<br />
New intermediate and new products derived there<strong>of</strong> are facing a major challenge: they<br />
must prove that they perform like their existing alternatives and/or they must provide<br />
significant health or environmental benefits.<br />
The production <strong>of</strong> carbohydrates from biomass is a technology which still <strong>of</strong>fers room for<br />
improvement. ADM is running a biorefinery for the conversion <strong>of</strong> lignocellulosic materials<br />
to sugars, which are the main source for new platform materials. Beside substances like<br />
Itaconic acid and Succinic acid Isosorbide is a promising molecule which can be used as<br />
platform chemical for a variety <strong>of</strong> products, i.e. polymers, solvents, surfactants etc., thus<br />
replacing e.g. Bisphenol A.<br />
ADM will continue to develop the use <strong>of</strong> biomass and assure feedstock supply by<br />
innovations in processing, investment in agricultural infrastructure, thus continuing and/or<br />
establishing partnerships.<br />
33
L15<br />
Isosorbide-based Value Products<br />
Claudia Stoer, Markus Dierker, Claus Nieendick, Catherine Breffa,<br />
BASF Personal Care and Nutrition GmbH, Düsseldorf, Germany<br />
claudia.stoer@basf.com<br />
Isosorbide, a cyclic diol completely obtainable from renewable raw materials, is an ideal<br />
candidate for further derivatization that should lead to new, innovative, green products with<br />
favourable properties regarding sustainability and performance compared to petrochemical<br />
based existing benchmarks.<br />
While Isosorbide has been known for many years, only a few applications have been<br />
realized commercially so far. When we started with Isosorbide chemistry we intended to<br />
evaluate Isosorbide as building block and starting material for the development <strong>of</strong> new<br />
marketable products for cosmetic and laundry detergents.<br />
Thus the challenge is that fundamental studies are required to come to a conclusion in<br />
terms <strong>of</strong> general and economic feasibility <strong>of</strong> the synthesis as well as compatibility with<br />
typical formulation ingredients. The properties <strong>of</strong> new synthesized derivatives are not<br />
predictable at all and must therefore be evaluated in a broad screening.<br />
Here the syntheses as well as first application test results <strong>of</strong> neutral and anionic Isosorbide<br />
derivatives are presented. In summary, not only the practicability in typical formulations but<br />
also the general suitability for the foreseen applications can be demonstrated. The most<br />
promising results are currently evaluated and optimized in new projects.<br />
34
L16<br />
Polyurethane dispersions based on renewable resource materials<br />
– <strong>of</strong>f to pasture new!<br />
Manfred Diedering, Markus Dimmers, Maria Ebert,<br />
Alberdingk Boley GmbH, Krefeld, Germany<br />
m.diedering@alberdingk-boley.de<br />
With the increasing importance to preserve limited resources and the steadily increasing<br />
prices for mineral oil based raw materials, the pressure and will is increasing to utilize<br />
more renewable raw materials. Among coating materials, alkyd resins and polyurethanes<br />
are important substance classes which can be produced to a significant percentage on a<br />
renewable base. Especially water-born polyurethane dispersions are predestined for the<br />
application in new fields <strong>of</strong> applications due to their broad variability regarding the<br />
chemical and mechanical properties.<br />
The binder in interior wall paints is typically on the base <strong>of</strong> styrene acrylics or vinyl acetate<br />
ethylene copolymers. These raw material bases make it quite difficult to switch to<br />
renewable raw materials as there are hardly any renewable monomers available. In<br />
addition, in this product range there are additional requirements and regulations important<br />
for a healthy living environment.<br />
Alberdingk Boley shows current developments in an area which is opening up a new<br />
application field for polyurethane dispersions: a binder for interior wall paints with a<br />
significant part <strong>of</strong> renewable raw material (based on vegetable oil) which is at the same<br />
time free <strong>of</strong> VOC (volatile organic compound) and amines. The presentation focuses on<br />
the application, technological comparison between conventional binders and the new<br />
product. It is shown that it is indeed possible to achieve comparable performance and to<br />
reduce the mineral oil based organic content by ca. 50%.<br />
35
L17<br />
Development <strong>of</strong> transformer oils based on renewable raw materials<br />
Günther Kraft, FUCHS Europe Schmierst<strong>of</strong>fe, Mannheim, Germany<br />
gunther.kraft@fuchs-europe.de<br />
Since approx. 20 years the increase <strong>of</strong> the usage <strong>of</strong> renewable material in substantial and<br />
energetical way is promoted by policy, natural sciences and economy. The increasing<br />
application <strong>of</strong> renewable raw materials has various positive consequences, <strong>of</strong> economical<br />
as well as <strong>of</strong> ecological nature. Fallow acres can be (re)used reasonably to produce<br />
renewable raw materials and the products basing on those are potentially less toxic and<br />
possess better biodegradability in comparison to mineral oil based products. Additionally<br />
the substitution <strong>of</strong> fossil limited resources, whose CO2- emissions potential pollutes the<br />
environment more distinctively, can have a positive effect on the eco-balance, as<br />
renewable raw materials <strong>of</strong>fer a closed cycle <strong>of</strong> materials.<br />
The development <strong>of</strong> new transformer oils on the base <strong>of</strong> plant oils <strong>of</strong>fer the possibility to<br />
substitute the hitherto used mineral oil based products. In addition to the higher<br />
biodegradability, the renewable based oils can be classified as “not hazardous to waters”<br />
according to German legislative, which is especially preferable in a sensible ambience.<br />
Besides the argumentation <strong>of</strong> sustainability and eco-balance, a renewable based ester<br />
transformer oil can also <strong>of</strong>fer technical benefits due to optimized properties. Examples are<br />
e.g. higher flame and burning points which can reduce the risk <strong>of</strong> the burning potential<br />
explicitly. Optimized cold temperature behaviour with a low pour point allows the<br />
application in cold locations, which is not possible with pure plant oils. In comparison to<br />
mineral oils, the ester based fluid is able to hold much higher quantities <strong>of</strong> water, without a<br />
decline <strong>of</strong> the electrical stability. Hereby the risk <strong>of</strong> snap-through failures at cold starting<br />
conditions is reduced. Due to the higher absorption <strong>of</strong> water by ester oils, the lifetime <strong>of</strong><br />
the transformer can be extended additionally, as the bio based oil decreases especially the<br />
hydrolytic degradation <strong>of</strong> the cellulose (by water) which is used in the transformer<br />
pressboard.<br />
Overall, new transformer ester oils on the base <strong>of</strong> renewable raw materials can have a<br />
share in the substitution <strong>of</strong> fossil crude materials without cutting back the technical abilities<br />
– in contrary, they outclass the mineral oil based transformer oils <strong>of</strong> today.<br />
36
L18<br />
Biorefinery: A sustainable design platform for green surfactants and<br />
s<strong>of</strong>t materials<br />
George John, Department <strong>of</strong> Chemistry,<br />
The City College <strong>of</strong> the City University <strong>of</strong> New York, New York, USA<br />
gglucose@gmail.com<br />
In future research, developing materials from renewable resources would be fascinating<br />
yet demanding practice, which will have a direct impact on industrial applications, and<br />
economically viable alternatives. This talk presents a novel and emerging concept <strong>of</strong><br />
generating new chemicals, intermediates and materials in a ‘Biorefinery’. Our continuous<br />
efforts in this area have led us to develop new amphiphiles and surfactants from industrial<br />
by-products, which upon self-assembly produced molecular materials including micelles,<br />
emulsions, lipid nanotubes, twisted/helical nan<strong>of</strong>ibers, thickening agents (molecular gels)<br />
and liquid crystals. More recently, harnessing the availability <strong>of</strong> ‘chiral pool’ <strong>of</strong><br />
carbohydrates and selectivity <strong>of</strong> enzymes catalysis, we have produced an array <strong>of</strong><br />
amphiphilic molecules from simple sugars and sugar alcohols. Intriguingly, by combining<br />
biocatalysis, with principles <strong>of</strong> green and supramolecular chemistry, we have developed<br />
building blocks-to-assembled materials. The second part <strong>of</strong> the talk addresses the<br />
templated synthesis <strong>of</strong> organic-inorganic hybrid materials for targeted use in coatings,<br />
liquid crystal templates and energy storage devices. These results will lead to efficient<br />
molecular design <strong>of</strong> supramolecular architectures and multifunctional s<strong>of</strong>t materials from<br />
underutilized plant/crop-based renewable feedstock.<br />
37
L19<br />
Synthesis <strong>of</strong> fatty ethers: Catalytic reduction <strong>of</strong> fatty acid esters<br />
Ursula Biermann, Jürgen O. Metzger,<br />
Universität Oldenburg and <strong>abiosus</strong> e.V., Oldenburg, Germany<br />
ursula.biermann@uni-oldenburg.de<br />
Oils and fats are presently the most important renewable feedstock <strong>of</strong> the chemical<br />
industry. The direct reduction <strong>of</strong> fatty esters and especially <strong>of</strong> triglycerides to fatty ethers<br />
would be a most important reaction because fatty ethers show interesting differences <strong>of</strong><br />
the properties in comparison to esters. We discuss a novel reaction protocol allowing to<br />
convert for example tributyryne, a triglyceride, and methyl oleate, an unsaturated fatty<br />
ester (Scheme) to the respective ethers using stoichometric amounts <strong>of</strong> 1,1,3,3-<br />
tetramethyldisiloxane (TMDS) as reductant and low catalyst loading <strong>of</strong> 1% GaBr 3 to give in<br />
a solvent-free reaction at room temperature after a reaction time <strong>of</strong> only 3 h 100 %<br />
conversion <strong>of</strong> the starting material and high product yields. The work up procedure is most<br />
simple. The products were isolated by simple distillation <strong>of</strong> the reaction mixture without any<br />
additional work-up.<br />
Using the described standard reaction conditions it was also possible to convert lactones<br />
to the respective cyclic ethers.<br />
O<br />
O<br />
+ TMDS/GaBr 3<br />
r. t., 3h<br />
O<br />
Conversion 100%; Yield 89% (distillation)<br />
Methyl oleate : TMDS : GaBr 3 =1:1:0.01<br />
Scheme: Gallium-catalyzed reduction <strong>of</strong> methyl oleate with tetramethyldisiloxane and<br />
GaBr 3 as catalyst to give methyl oleylether<br />
[1] WO 2013/010747 A1<br />
38
L20<br />
Additions to unsaturated fatty acid esters: Electrophilic additions via<br />
boron compounds and [2+2]-cycloadditions with<br />
N-chlorosulfonylisocyanate to ß-lactams<br />
Theodor Lucas, Christian Kalk, Hans J. Schäfer, Organisch- chemisches Institut der<br />
Universität Münster, Münster, Germany<br />
schafeh@uni-muenster.de<br />
Unsaturated fatty acids can be modified by electrophilic addition and cycloaddition to form<br />
higher value products.<br />
In hydroboration the added boron atom can be replaced in a subsequent oxidation by a<br />
hydroxy group [1]. This way methyl linoleate (1), methyl ricinoleate (2), methyl 10-<br />
undecenoate (3) and methyl oleate (4) could be converted into the corresponding methyl<br />
dihydroxy- and hydroxystearates and 11-hydroxyundecenoate in 82-92 % yield [2].<br />
Organoboranes isomerize at higher temperatures [1]. Hydroboration <strong>of</strong> oleic acid and<br />
subsequent heating to 220 oC led after oxidative work-up to 70% <strong>of</strong> 1,4-octadecandiol [2].<br />
Presumably a 1,4-oxaborinane intermediate determines the interesting regioselectivity <strong>of</strong> this<br />
isomerization.<br />
Organoboranes undergo a dealkylation-coupling with alkaline silver nitrate, presumably via<br />
radicals as intermediates, which had been applied to ester 3 [1]. Attempts to transfer the<br />
reaction to the internal organoboranes from ester 1 and 4 led to radical disproportionation<br />
products, which is the favourable reaction <strong>of</strong> the intermediate secondary alkyl radicals.<br />
Reaction <strong>of</strong> ester 3 with a terminal double bond and 1-hexene, which invlolves primary alkyl<br />
radicals, led to 25 % <strong>of</strong> the heterocoupling product: methyl heptadecanoate [2].<br />
Organoboranes can be added to α,β-unsaturated carbonyl compounds [1]; presumably a<br />
radical chain reaction is involved. With 3, borane and methylvinylketone the 1,4-adduct<br />
methyl 14-oxopentadecanoate could be obtained in 68% yield [2]. However, attempts to add<br />
unsaturated fatty acid methyl esters with internal double bonds as 1 and 4 failed.<br />
With carbon monoxide or the cyanide anion the carbonyl group can be inserted between two alkyl<br />
groups <strong>of</strong> an organoborane. The same result can be achieved in the base initiated reaction <strong>of</strong><br />
dichloromethyl methyl ether (DCME) with boranes. This is a less toxic alternative to the use <strong>of</strong><br />
carbon monoxide or cyanide and additionally it has a broader scope [1]. The boranes <strong>of</strong> 1, 3 and 4<br />
were treated at -75°C with DCME and then were deprotonated with lithium triethyl carboxide. This<br />
way esters 1, 3 and 4 led to dimers connected by a carbonyl group in 55-80% yield [2].<br />
The [2+2]-cycloaddition <strong>of</strong> N-chlorosulfonylisocyanate (NCSI) to alkenes affords ß-lactams<br />
[3]. The esters 1, 2, 3 and methyl petroselinate (5) were reacted at room temperature with<br />
NCSI. Thereafter the chlorosulfonyl group was reductively removed with sodium disulfite,<br />
which afforded the ß-lactams in 59-72% yield [4].<br />
Ring opening <strong>of</strong> the ß-lactams led to partial ester hydrolysis in spite <strong>of</strong> using different acids<br />
and different acid concentrations. To achieve a selective ring opening the ester group was<br />
replaced by an acid resistant alkoxy group. Alkoxy ethers from 3 and 4 afforded the ß-lactams in<br />
42-57% yield; the lactams were hydrolyzed with aqueous HCl quantitatively to the corresponding<br />
amino acids.<br />
The antibiotic activity <strong>of</strong> the ß-lactams from 2, 3 and 5 was explored with the plate diffusion<br />
test. They showed a significant activity against mycobacterium, which also comprises the<br />
pathogens <strong>of</strong> tuberculosis and leprosy. The highest activity was found with the ß-lactam from 5.<br />
[1] H. C. Brown, Hydroboration, 2. ed, Benjamin, 1980.<br />
[2] Th. Lucas, Ph. D. Thesis, University <strong>of</strong> Münster, 1991.<br />
[3] R. Graf, Chem. Ber. 1956, 89, 1071-1079.<br />
[4] Ch. Kalk, Ph. D. Thesis , University <strong>of</strong> Münster, 2001.<br />
39
L21<br />
Singlet oxygenation <strong>of</strong> unsaturated monoglycerides in single-phase and<br />
multiphase systems using hydrogen peroxide catalyzed by molybdate<br />
anions<br />
Hermine HNM NSA MOTO, Zephirin MOULOUNGUI, Université de Toulouse, ENSIACET-<br />
INRA-INP Toulouse, Laboratoire de Chimie Agro-Industrielle, Toulouse, France<br />
hermine.nsamoto@ensiacet.fr<br />
Monoglycerides are the most polar component <strong>of</strong> simple lipids. Because <strong>of</strong> their special<br />
chemical structures comprising an aliphatic lipophilic chain and two hydroxyl groups in the<br />
hydrophilic part, monoglycerides have detergent-like properties; hence, they easily form<br />
micelles in aqueous solutions. Monoglycerides are directly used in a wide range <strong>of</strong><br />
applications, including surfactants, lubricant additives, plastics, and materials for textile<br />
industry. These products are <strong>of</strong> great interest as emulsifiers in the foods, cosmetic and<br />
pharmaceutical industries. Monoglycerides have been synthesized by a variety <strong>of</strong><br />
substrates with glycerol, an abundant by-product from the biodiesel industries (1). Our<br />
research group has already developed new routes to convert the glycerol and glycidol with<br />
fatty acid material to 1-monoglycerides (2,3). This fact stimulated the study on<br />
monoglyceride as a platform chemical that can be derivatized to design new functional<br />
building-blocks for the synthesis <strong>of</strong> new surfactants or polymers.<br />
The major aim <strong>of</strong> this project is to use vegetable oils and their derivatives, and to transform<br />
them by the simple methods into very rewarding oxygenated products which are products<br />
<strong>of</strong> high added value oleochemicals. To do this, the oxidation <strong>of</strong> unsaturated fatty acids by<br />
singlet oxygen has proved to be considerable more suitable route to the synthesis <strong>of</strong> the<br />
allylic alcohols and epoxides compounds (4).<br />
First, this presentation will highlights a new route to convert selectively double bond <strong>of</strong><br />
unsaturated monoglycerides into oxygenated monoglycerides using singlet oxygen<br />
generated chemically by aqueous hydrogen peroxide (H2O2) catalyzed by molybdate<br />
anions (MoO42-) in single-phase and multiphase emulsion systems (5,6). Such a method<br />
involves the synthesis in an organized molecular system which is favorable to in situ<br />
production <strong>of</strong> singlet oxygen and to improve the lifetime <strong>of</strong> singlet oxygen and the<br />
coexistence <strong>of</strong> singlet oxygen with a molybdate catalyst activated. According to this<br />
process, the hydroxy allylic-, epoxy- and dihydroxy-monoglycerides were synthesized and<br />
the characteristics <strong>of</strong> these resultant products were evaluated.<br />
Second, this presentation will present the use <strong>of</strong> a method for in situ generation <strong>of</strong> singlet<br />
oxygen by heterogeneous molybdate-based catalysts which are consisting with molybdate<br />
anions supported on anion exchange resins. This system can be considered as an<br />
emulsion or a microemulsion supported on a solid catalytic phase that prevent only the<br />
close contact between organic substrates and peroxomolybdates (the intermediate<br />
peroxomolybdates generated by H2O2/MoO42- system) to increase the in situ generation<br />
<strong>of</strong> singlet oxygen and promotes also a large surface exchange for oxidation.<br />
The last part <strong>of</strong> study deals with the synthesis <strong>of</strong> estolides (7), where oleic acid and erucic<br />
acid and the new oxygenated monoglycerides were used as model substrate. All reactions<br />
were run at stoichiometry such that the fatty acids hydroxyl groups would all be esterified<br />
to estolide. Using this approach, chemical characteristics <strong>of</strong> these new estolides<br />
compounds were also analyzed.<br />
40
L22<br />
Synthesis <strong>of</strong> biobased building blocks from vegetable oils: towards<br />
platform chemicals<br />
Sylvain Caillol, Remi Auvergne, Bernard Boutevin,<br />
ICGM - ENSCM, Montpellier, France<br />
sylvain.caillol@enscm.fr<br />
Uncertainty in terms <strong>of</strong> price and availability <strong>of</strong> petroleum, in addition to global political and<br />
institutional tendencies toward the principles <strong>of</strong> sustainable development, urge chemical<br />
industry to a sustainable chemistry and particularly the use <strong>of</strong> renewable resources in<br />
order to synthesize biobased chemicals and products. A biobased product is a product<br />
synthesized from renewable resources (vegetal, animal, or fungal). Vegetable oils come<br />
from various plants (soybean, palm, rapeseed, etc.) and mainly contain triglycerides<br />
molecules where the three hydroxyl functions <strong>of</strong> glycerin are esterified with fatty acids.<br />
These fatty acids could be saturated, with non-reactive aliphatic chains (stearic or palmitic<br />
acids) or unsaturated, with aliphatic chains bearing double bonds (oleic, linoleic, linolenic,<br />
ricinoleic acid, etc.). These natural oils, and particularly the unsaturated ones, are <strong>of</strong><br />
interest since various reactions could be performed from their different groups in order to<br />
obtain various building blocks for polymer chemistry. We report the synthesis <strong>of</strong> various<br />
building blocks from vegetable oils in one or two-steps syntheses. Thiol-ene coupling<br />
allowed to synthesize new biobased reactants with various function and functionality with<br />
reaction conditions in agreement with green chemistry principles: it does not use neither<br />
solvent nor initiator or need a simple purification step, feasible at industrial scale.<br />
Esterification and amidification were also use to insert ester or amide groups in fatty<br />
chains in order to modifiy properties <strong>of</strong> there<strong>of</strong> synthesized polymers. Building blocks<br />
synthesized have various functions and functionality: polyols, polyacids, polyamines and<br />
dicyclocarbonates from vegetable oils and from glycerine derivatives.<br />
We developed a real chemical toolbox based on thiol-ene coupling and<br />
amidification/esterification to synthesize a library <strong>of</strong> biobased building blocks with various<br />
functions and functionality from vegetable oils. The synthesized building blocks reported in<br />
this contribution are polyols, polyacids, polyamines and dicyclocarbonates from vegetable<br />
oils and from glycerine derivatives. They led to polymer synthesis such as polyurethanes,<br />
polyhydroxyurethanes and epoxy resins. These biobased building blocks led to polymers<br />
with various properties: low Tg polymers for coating or higher Tg polymers for composites.<br />
41
L23<br />
Biobased Polyamides past, present and future<br />
Jürgen Herwig, Jasmin Nitsche, Harald Häger, Evonik, Marl, Germany<br />
juergen.herwig@evonik.com<br />
Although the chemical industry stands for less than 10 percent <strong>of</strong> the overall fossil carbon<br />
usage, the chemical industry is nevertheless making a concerted effort to use renewable<br />
resources for producing the monomers used in polymer synthesis. One method is to use<br />
ethanol obtained from sugar cane (as Braskern and DOW are planning to do in Brazil) to<br />
manufacture petrochemical feedstocks such as ethylene, which can then be used for<br />
synthesizing polyethylene. The advantage <strong>of</strong> this method is that it can accommodate<br />
existing processes, and does not affect existing approvals. A second approach—one that,<br />
while significantly more difficult, is also more promising in the long run—is to convert raw<br />
materials using new catalytic or biotechnological processes. This is the strategy that<br />
DuPont is pursuing as it uses biotechnology techniques to produce 1,3-propandiol, a<br />
compound that yields new material properties in polyesters. While reducing the number <strong>of</strong><br />
process steps—in some cases dramatically—is yet another advantage, these new<br />
materials will, however, need to be relaunched on the market and submitted to relevant<br />
chemical registries.<br />
Polyamids based on biorenewable feedstocks, primarily those derived from ricinus oil<br />
and/or ricinoleic acid methyl ester, have been<br />
known for over 50 years.<br />
Boiling with NaOH yields<br />
sebacic acid, and pyrolytic cleavage at >500ºC<br />
High<br />
produces 10-undecylenic<br />
PEEK,<br />
acid. This, in turn, can be<br />
PPSU, performance<br />
converted to 11- PEI, PPA, Bio- polymers aminocarboxylic acid and<br />
PA12 PPA<br />
PA11. Decanediamine PA11<br />
can also be synthesized in<br />
PA1012<br />
this way, which opens up<br />
the door to producing<br />
PA1010,<br />
PA1010. Combining these<br />
PMMA, PA6, PA610, Engineering with monomers derived<br />
PA66, PBT,<br />
plastics<br />
from petrochemical PET, PC PTT, etc<br />
feedstocks yields<br />
polyamides such as PA610, PA1012 and<br />
PP, PS, PE, PE, PVC, PLA,<br />
PA10T based in part on PVC, etc.<br />
biological sources. It is<br />
PHB, etc<br />
important to remember Based on petrochemical<br />
feedstock renewable feedstock above necessarily<br />
Based on bio-<br />
here that the synthesis<br />
pathways described<br />
produce by-products.<br />
Major growth in the use <strong>of</strong> polyamides derived from petrochemical feedstocks has<br />
prompted growing interest in sustainable products over the past several years, with the<br />
result that more and more fatty acid-based polyamides are being marketed as<br />
biopolyamides. This means that polyamides from biorenewable feedstocks are now an<br />
issue for the future—the task ahead will be to combine the sustainability <strong>of</strong> renewable<br />
materials with the manufacturing processes <strong>of</strong> the petrochemical industry.<br />
In addition to discussing methods for synthesizing polyamides from a variety <strong>of</strong> available<br />
monomers, the speaker will also compare the properties <strong>of</strong> polyamides derived from<br />
biorenewable feedstocks to those <strong>of</strong> their petrochemical counterparts. How can<br />
sustainability and green chemistry be combined? Various approaches will be presented.<br />
42
L24<br />
Plant oil based renewable Polyamide monomers and their polymers via<br />
efficient (catalytic) processes<br />
Matthias Winkler, Oğuz Türünç, M. A. R. Meier, KIT, Karlsruhe, Germany<br />
matthias.winkler@kit.edu<br />
Aliphatic polyamides are a class <strong>of</strong> highly valuable engineering plastics. Their excellent<br />
mechanical properties are mainly due to increased chain-chain interactions by hydrogen<br />
bonding, which lead to higher tensile strength, impact strength, fracture stress and<br />
abrasive resistance as well as chemical inertness and heat resistance. Polyamides are<br />
widely applied high-performance polymers, which are used, e.g., as fibers, tubings, formparts<br />
in the automobile-, textile- or electric industry. Particularly, Polyamides from<br />
renewable resources are <strong>of</strong> great interest due to their lower environmental impact.<br />
Herein, we present three different strategies for the synthesis <strong>of</strong> AB-type renewable<br />
monomers, which can be used for the preparation <strong>of</strong> polyamides by simple<br />
polycondensation. In this context, methyl oleate and -erucate were utilized as substrates,<br />
which were transformed to valuable AB-type monomers via thiol-ene addition <strong>of</strong><br />
cysteamine[1] and other efficient procedures.[2,3] Both, monomer synthesis and<br />
polymerization were studied in detail and the resulting Polyamides were characterized by<br />
GPC, NMR, DSC as well as tensile tests. Moreover, the prepared renewable monomers<br />
were employed in co-polymerizations with hexamethylendiamine and dimethyl adipate to<br />
modify the mechanical and thermal properties <strong>of</strong> conventional nylon 6,6.<br />
[1]O. Türünç, M. Firdaus, G. Klein, M. A.R. Meier, Green. Chem. 2012, 14, 2577-2583.<br />
[2]M. Winkler, M. A. R. Meier, submitted<br />
[3]M. Winkler, M. Steinbiß, M. A. R. Meier, submitted<br />
43
L25<br />
Dimer fatty acids: Building blocks for a multitude <strong>of</strong> new<br />
macromolecular architectures<br />
Luc Averous, ICPEES-ECPM University <strong>of</strong> Strasbourg, France<br />
luc.averous@unistra.fr<br />
At high temperature, double bonds <strong>of</strong> unsaturated fatty acids may change their position to<br />
form conjugated structures, facilitating their dimerisation by Diels-Alder mechanism. This<br />
reaction leads to a mixture <strong>of</strong> compounds, such as dimers and trimmers <strong>of</strong> fatty acids.<br />
After purification, the dimer fatty acids can be used as raw materials or modified e.g., for<br />
the synthesis <strong>of</strong> biobased polymers.<br />
The activity <strong>of</strong> the BioTeam at University <strong>of</strong> Strasbourg (France) is mainly focused on the<br />
development <strong>of</strong> new biobased polymer systems for environmental and biomedical<br />
applications. In this context, we have developed a great variety <strong>of</strong> new macromolecular<br />
architectures based on dimer fatty acids such as (i) TPUs, which can be partially [1-2] <strong>of</strong><br />
fully biobased [3], (ii) Polyamides [4-5], (iii) polyetheramides …<br />
The presentation will be mainly focused on the structure-properties relationships for these<br />
different architectures, in connection with theirs synthesis.<br />
From these polymers, different multiphase systems (biocomposites …) can be formulated<br />
[6-8] with specific performances to fulfill the requirements <strong>of</strong> a large range <strong>of</strong> applications<br />
and numerous fields such as automotive industry, consumer or domestic equipment,<br />
construction engineering and biomedical applications.<br />
1. Bueno-Ferrer C., Hablot E., Garrigós M.C., Bocchini S., Averous L., Jiménez A., (2012)<br />
“Relationship between morphology, properties and degradation parameters <strong>of</strong> novative<br />
biobased thermoplastic polyurethanes obtained from dimer fatty acids” Polymer<br />
Degradation and Stability. Vol. 97, N°10, pp. 1964-1969.<br />
2. Bueno-Ferrer C., Hablot E., Perrin-Sarazin F., Garrigós M.C., Jiménez A., Averous L.<br />
(2012) “Structure and morphology <strong>of</strong> new bio-based thermoplastic polyurethanes obtained<br />
from dimeric fatty acids" Macromolecular Materials & Engineering. Vol. 297, N°8, pp. 777–<br />
784.<br />
3. Charlon M., Heinrich B., Donnio B., Matter Y., Avérous L., “Synthesis, structure and<br />
properties <strong>of</strong> fully biobased thermoplastic polyurethanes based on hydrogenated dimer <strong>of</strong><br />
fatty acids “ Under Press.<br />
4. Hablot E., Donnio B., Bouquey M., Avérous L. (2010) « Dimer acid-based thermoplastic<br />
bio-polyamides: reaction kinetics, properties and structure ». Polymer, Vol. 51, N°25, pp.<br />
5895-5902.<br />
5. Hablot E., Tisserand A., Bouquey M., Avérous L. (2011) “Accelerated artificial ageing <strong>of</strong><br />
new dimer fatty acid-based polyamides” Polymer Degradation and Stability. Vol. 96, pp.<br />
1097-1103.<br />
6. Matadi R., Hablot E., Wang K., Bahlouli N., Ahzi S., Avérous L. (2011) « High strain rate<br />
behaviour <strong>of</strong> renewable biocomposites based on dimer fatty acid polyamides and cellulose<br />
fibres » Composites Science and Technology. Vol. 71, pp. 674–68.<br />
7. Hablot E, Matadi R, Ahzi S, Avérous L. (2010) “Renewable biocomposites <strong>of</strong> dimer fatty<br />
acid-based polyamides with cellulose fibres: thermal, physical and mechanical properties”.<br />
Composites Science and Technology. Vol. 70, pp. 504–509.<br />
8. Hablot E, Matadi R, Ahzi S, Vaudemond R, Ruch D, Avérous L. (2010) “Yield behaviour<br />
<strong>of</strong> renewable biocomposites <strong>of</strong> dimer fatty acid-based polyamides with cellulose fibres”.<br />
Composites Science and Technology. Vol. 70, pp. 525–529.<br />
44
L26<br />
Enzyme-catalyzed reactions for fatty acids modification<br />
Pierre Villeneuve, Erwann Durand, Jérôme Lecomte, Eric Dubreucq<br />
UMR IATE, CIRAD, Montpellier, France<br />
villeneuve@cirad.fr<br />
This presentation will give an overview <strong>of</strong> the various kinds <strong>of</strong> reactions that are carried out<br />
in our research group regarding the use <strong>of</strong> enzymes, mainly lipases, to modify oils and<br />
fats. Lipases are enzymes that perform very well outside their physiological and natural<br />
medium and that can be therefore used as biocatalysts for reactions in limited aqueous<br />
systems. Indeed, lipases are widely used in a large variety <strong>of</strong> reactions such as lipid<br />
customizing, corresponding to an adjustment <strong>of</strong> the fatty acid composition and<br />
regiodistribution <strong>of</strong> oils and fats to obtain new products with designed physical and<br />
chemical properties, such as mixtures enrichment and modification <strong>of</strong> fatty acids or such<br />
as the synthesis <strong>of</strong> new lipophilized compounds with specific physico-chemical or<br />
biological properties. Some examples <strong>of</strong> such reactions will be given with emphasis on<br />
lipases specificity and selectivities, and the use <strong>of</strong> new alternative media to organic<br />
solvents for enzyme-catalyzed reactions<br />
45
L27<br />
Fine-tuning fatty acids length chain by metabolic engineering for<br />
“Single Cell Oils” strategies in Ashbya gossypii<br />
Rodrigo Ledesma-Amaro, José Luis Revuelta,<br />
Universidad de Salamanca, Salamanca, Spain<br />
rodrigoledesma@usal.es<br />
Fatty acids and its derivatives are highly relevant compounds in industry since they have a<br />
wide range <strong>of</strong> applications, from bi<strong>of</strong>uels to fine chemicals such as pharmaceutical or<br />
fragrances. Metabolic engineering <strong>of</strong> microorganisms to produce “Single Cell Oils” (SCOs)<br />
seems to be a feasible strategy with promising industrial results in lipid production. Ashbya<br />
gossypii is an industrial-friendly filamentous fungus, which is being used for large-scale<br />
production <strong>of</strong> vitamins but it is also an oleaginous organism able to accumulate lipids up to<br />
40% <strong>of</strong> its cell dry weight. Different organisms have distinct fatty acids compositions and<br />
two kinds <strong>of</strong> enzymes: elongases and desaturases are major determinants <strong>of</strong> lipid pr<strong>of</strong>iles.<br />
We characterized the elongase and desaturase system in Ashbya gossypii by<br />
heterologous functional analysis in S. cerevisiae, thus we identified two very long chain<br />
fatty acid elongases and one ∆12 desaturase. We used this information to perform<br />
metabolic engineering in this pathway and several Ashbya gossypii strains with different<br />
fatty acid composition were constructed. These strains can be used as both, 1) platform<br />
strains for future development <strong>of</strong> genetic engineering approaches in order to produce an<br />
specific fatty acid derivative and 2) as direct source <strong>of</strong> uncommon fatty acids important for<br />
industry since they are enriched in 24:0 and 26:0 or 24:1, which are mainly constituents <strong>of</strong><br />
wax esters used for polishes, coatings and cosmetics or they are used as hightemperature<br />
lubricants and engineering nylons respectively.<br />
46
L28<br />
Bio-catalytic synthesis <strong>of</strong> small molecule oil structuring agents from<br />
renewable resources<br />
Julian Silverman, George John,<br />
Department <strong>of</strong> Chemistry, The City College <strong>of</strong> New York, and The Graduate Center <strong>of</strong> The<br />
City University <strong>of</strong> New York, New York, New York,USA<br />
jsilverman@gc.cuny.edu<br />
The synthesis and formation <strong>of</strong> functional materials from renewable resources is the first<br />
step to mitigating an anthropogenic dependence on petroleum-derived products.<br />
Biocatalysis allows for the facile synthesis <strong>of</strong> fatty acid glucosides capable <strong>of</strong> thickening<br />
and solidifying a range <strong>of</strong> hydrophobic solvents. Various glucosides were selected as<br />
sugar-based headgroups and a series <strong>of</strong> amphiphiles were synthesized by attaching<br />
hydrophobic carboxylic acids at one-end <strong>of</strong> the sugar using an enzyme-mediated<br />
regioselective transesterification reaction. For tuning the hydrophobicity <strong>of</strong> the resulting<br />
amphiphile, various carboxylic acids <strong>of</strong> different chain length were attached [typically<br />
(CH2)4-14]. A library <strong>of</strong> new compounds was easily established by the simple variation <strong>of</strong><br />
hydrophobic fatty acid chain length, and modification <strong>of</strong> the hydrophilic glucoside for a<br />
variety <strong>of</strong> applications (food storage and preservation, cosmetics and personal care<br />
products). The synthesis <strong>of</strong> novel structuring agents using biocatalysis from renewable<br />
feedstocks is a green methodology that may be used to produce next generation<br />
environmentally benign products and chemicals.<br />
47
L29<br />
Online analysis <strong>of</strong> polycondensations in a bubble column reactor using<br />
ATR-FTIR spectroscopy<br />
Jakob Gebhard, Lutz Hilterhaus, Andreas Liese,<br />
University <strong>of</strong> Technology <strong>of</strong> Hamburg, Hamburg, Germany<br />
Jakob.Gebhard@tuhh.de<br />
Synthetic polymers are indispensable for modern society. Since the 1920s polymers are<br />
produced from fossil resources, which are being exhausted. Biocatalytic syntheses <strong>of</strong><br />
polymers via lipase-catalyzed polycondensation <strong>of</strong> renewable monomers is a alternative<br />
but challenging approach. However biocatalysts show higher enantio- and regioselectivity<br />
at lower reaction temperatures than chemical catalysts.<br />
The presented work focuses on the solvent free polyester synthesis starting from 1,3-<br />
propanediol and 9-((Z)-non-3-enyl)-10-octylnonadecanedioic acid (PripolTM) in a bubble<br />
column reactor catalyzed by immobilized lipase B from Candida antarctica. The analysis <strong>of</strong><br />
these biotransformations is usually carried out by size exclusion chromatography.<br />
Therefore monitoring <strong>of</strong> such processes requires labor intensive sample preparation. The<br />
aim <strong>of</strong> this work is to design chemometric models based on the measured absorption<br />
spectra <strong>of</strong> fourier transform infrared (FTIR) spectroscopy in combination with an<br />
attenuated total reflectance (ATR)-probe. This methodology allows the continuous<br />
determination <strong>of</strong> conversion <strong>of</strong> the reactants as well as the molecular weight (Mw)<br />
distribution <strong>of</strong> the formed polymer. The developed models make use <strong>of</strong> partial least<br />
squares (PLS) algorithm to correlate <strong>of</strong>fline data and spectral information. Mw and<br />
conversion from several polymerizations performed at same experimental conditions are<br />
used to calibrate two independent models, which showed small root mean square errors <strong>of</strong><br />
cross validation <strong>of</strong> 2,14 % and 319 g/mol for conversion and Mw respectively.<br />
48
L30<br />
Application <strong>of</strong> fatty acid chlorides in iron and zinc catalyzed<br />
depolymerization reactions<br />
Stephan Enthaler, TU Berlin, Department <strong>of</strong> Chemistry, Cluster <strong>of</strong> Excellence “Unifying<br />
Concepts in Catalysis”, Berlin, Germany<br />
stephan.enthaler@tu-berlin.de<br />
Polymers occupy a significant and omnipresent position in human life. Current polymer<br />
feedstocks are based primarily on monomers originated from fossil fuels, which cause<br />
clearly a number <strong>of</strong> problems. On the one hand the confirmed reserves <strong>of</strong> fossil fuels are<br />
progressively decreasing, and their depletion is just a matter <strong>of</strong> time. On the other hand a<br />
huge quantity <strong>of</strong> polymers is thermally decomposed after they have accomplished their<br />
purposes or are converted to low-quality materials. In consequence, a negative impact on<br />
the environment is caused, specifically the production <strong>of</strong> greenhouse gases. Due to these<br />
problems, an important issue for current research must address to the invention <strong>of</strong><br />
protocols for an efficient recycling <strong>of</strong> polymers. One attractive approach could be the<br />
depolymerization <strong>of</strong> polymeric materials to attain valuable products, which can applied<br />
later on in polymerization processes to produce new polymeric materials. In this regard the<br />
utilization <strong>of</strong> transition metal catalysts presents an efficient opportunity to realize this aim.<br />
Here the application <strong>of</strong> cheap and abundant “bio”metals as catalyst core (e.g., Fe, Zn) will<br />
be advantageous. An extensively applied class <strong>of</strong> polymers or co-polymers are polyethers<br />
(e.g., polytetrahydr<strong>of</strong>uran, polyethylene oxide, polypropylene oxide). The repeating ether<br />
units could represent an appropriate functionality to coordinate to the metal and by this an<br />
activation <strong>of</strong> the ether can take place. The addition <strong>of</strong> fatty acid chlorides, to the activated<br />
ether functionality could allow the depolymerization <strong>of</strong> the polyether to obtain well-defined<br />
monomeric chloroesters. The products can be suitable sources for the production <strong>of</strong><br />
monomers, such as vinyl esters, which can later on polymerize to yield new high-quality<br />
semi-biomaterials. Moreover, the carbon carbon double bonds in unsaturated fatty acids<br />
can be <strong>of</strong> interest for cross linked polymers.<br />
Based on this concept and our interest in zinc and iron chemistry we present herein the<br />
usefulness <strong>of</strong> an easy-to-adopt system composed <strong>of</strong> catalytic amounts <strong>of</strong> zinc or iron salts<br />
and stoichiometric amounts <strong>of</strong> fatty acid chlorides for the depolymerization <strong>of</strong> polyethers to<br />
yield valuable building blocks for polymer chemistry.[1-4]<br />
References<br />
[1] S. Enthaler, M. Weidauer, Catal. Lett. 2012, 142, 168–175.<br />
[2] S. Enthaler, M. Weidauer, Chem. Eur. J. 2012, 18, 1910–1913.<br />
[3] S. Enthaler, M. Weidauer, ChemSusChem 2012, 5, 1195–1198.<br />
[4] S. Enthaler, Eur. J. Lipid Sci. Technol. 2012, DOI: 10.1002/ejlt.201200301.<br />
49
L31<br />
Synthesis <strong>of</strong> palm oil based ethylhexyl ester for drilling fluid application<br />
Robiah Yunus, Nur Saiful Hafiz Habib, Zurina Zainal Abidin,<br />
Universiti Putra Malaysia, Selangor, Malaysia<br />
robiah@eng.upm.edu.my<br />
Recently, the use <strong>of</strong> ester as a base fluid in synthetic base fluids (SBF) has become a<br />
trend in drilling operations due to many advantages compared to the conventional drilling<br />
fluids in particular its costs and environmental concern. The synthesis <strong>of</strong> ester as<br />
biodegradable base oil was conducted via transesterification reaction <strong>of</strong> palm oil methyl<br />
ester (POME) with 2-ethylhexanol (EH). The reaction was carried out at different<br />
temperatures (70⁰C to 140⁰C) and the pressure was fixed at 1.5 mbar. Palm oil based<br />
ethylhexyl esters was successfully synthesized in less than 30 minutes under 1.5 mbar<br />
pressure, 70ºC, and 1:2 molar ratio <strong>of</strong> POME to EH. The rate constant <strong>of</strong> the reaction (k)<br />
obtained from the kinetics study was in the range <strong>of</strong> 0.44 to 0.66 s-1. The activation energy<br />
<strong>of</strong> the reaction was 15.6 kJ.mol-1. The preliminary investigation on the lubrication<br />
properties <strong>of</strong> drilling mud formulated with palm based 2EH ester indicated that the base oil<br />
has a great potential to substitute the synthetic ester base oil for drilling fluid. Its high<br />
kinematic viscosity provides better lubrication to the drilling fluid compared to other esterbased<br />
oils. The pour point and the flash point are superior for the drilling fluid formulation.<br />
The plastic viscosity, HPHT filtrate loss and emulsion stability <strong>of</strong> the drilling fluid give<br />
acceptable values while, gel strength and yield point can be improved by blending it with<br />
proper additives.<br />
50
L32<br />
Biobased adhesives: when green chemistry meets the material science<br />
<strong>of</strong> sticky things<br />
Richard Vendamme,<br />
Nitto Denko Corporation's European Research Committee (ERC), Nitto Europe NV,<br />
Belgium<br />
richard.vendamme@neuf.fr<br />
The growing awareness <strong>of</strong> society towards environmental issues combined with the recent<br />
governments regulations and incentives towards the reduction <strong>of</strong> carbon dioxide emissions<br />
is pushing the chemical and adhesive industries to develop greener products and to find<br />
alternative growth strategies based on more sustainable economical models. Although the<br />
use <strong>of</strong> raw materials derived from renewable feedstock seems a particularly relevant<br />
option, finding sustainable and efficient ways to transform bi<strong>of</strong>eedstocks into highly<br />
functional materials and coatings is still very challenging.<br />
Pressure sensitive adhesive (PSA) materials are a peculiar class <strong>of</strong> glues intended to form<br />
a reversible bond simply by the application <strong>of</strong> a light pressure to marry the adhesive with<br />
the adherent. Conceptually, PSAs must be designed with a subtle balance between flow<br />
and resistance to flow: the bond forms because the adhesive is s<strong>of</strong>t enough to wet the<br />
adherent, but the bond also has suitable strength because the adhesive is hard enough to<br />
resist the stress <strong>of</strong> the debonding stage. The formation, development and strength <strong>of</strong> the<br />
adhesive bonds can be tuned by thoughtfully adjusting the bulk viscoelastic properties <strong>of</strong><br />
the glue and/or by incorporating functional monomers within the base-polymer structure.<br />
To date, most commercial PSA are still based on petroleum resources and there is an<br />
imperious need to develop more sustainable PSA chemistries.<br />
The development <strong>of</strong> biobased materials is one solution (among others) used by the Nitto<br />
Denko group to tackle environmental problems. In this talk, we would like to demonstrate<br />
that Nitto Denko’s ambition to make a step-forward in the advancement <strong>of</strong> biobased<br />
adhesives take the form <strong>of</strong> pragmatic and multi-angle investigations covering both value<br />
chain considerations (monitoring and screening <strong>of</strong> biobased raw material, performing Life-<br />
Cycle-Assessment), technical aspects (leveraging the performance and reliability <strong>of</strong><br />
biobased adhesives) and new business development (unravelling the full business<br />
potential <strong>of</strong> biobased adhesives). The technical part <strong>of</strong> the presentation will be focused on<br />
the development <strong>of</strong> polyester-based pressure sensitive adhesives derived from various<br />
renewable bi<strong>of</strong>eedstocks such as plant oils or sugars.1<br />
1 Interplay Between Viscoelastic and Chemical Tunings in Fatty-Acid-Based Polyester<br />
Adhesives: Engineering Biomass toward Functionalized Step-Growth Polymers and S<strong>of</strong>t<br />
Networks. R. Vendamme*, K. Olaerts, M. Gomes, M. Degens, T. Shigematsu, W. Eevers,<br />
Biomacromolecules, 13, 1933-1944 (2012).<br />
51
L33<br />
Microwave-assisted heterogeneous catalysis in esterification and<br />
etherification reactions<br />
Sabine Valange 1 , Gina Hincapie 2 , Diana Lopez 2 , Clement Allart 1 , Joel Barrault 1 ,<br />
1<br />
IC2MP, UMR CNRS 7285, ENSIP, Poitiers Cedex, France ; 2 Institute <strong>of</strong> Chemistry,<br />
University <strong>of</strong> Antioquia, Medellin, Colombia<br />
joel.barrault@univ-poitiers.fr<br />
Among alternative fuels, monoalkyl (methyl or ethyl) esters issued from vegetable or<br />
animal oils and alcohols have some advantages, such as renewability, biodegradability,<br />
heat content, availability, … From these natural oils (triesters <strong>of</strong> glycerol) monoalkyl-esters<br />
are obtained via transesterification with methanol or ethanol, while glycerol being formed<br />
as by-product. The use <strong>of</strong> methanol is more common than ethanol at the industrial scale<br />
because <strong>of</strong> its low cost and high reactivity. There is however an increased interest in the<br />
use <strong>of</strong> ethanol because <strong>of</strong> its superior solubility for oil coupled to its entirely renewable<br />
characteristics. Since the reaction rate <strong>of</strong> that reaction is much lower than the former one,<br />
there is a need for finding more efficient catalysts or/and more efficient processes.<br />
We have shown that starting from a non-edible oil, namely castor oil obtained from Ricinus<br />
communis L. seeds, a homogeneous base-catalyzed transesterification process in the<br />
presence <strong>of</strong> ethanol can take place at low temperature (60°C) and atmospheric pressure<br />
with a ethyl-ester yield <strong>of</strong> 78% after 1h <strong>of</strong> reaction. By contrast, the use <strong>of</strong> microwaves as a<br />
heating medium to drive the transesterification reaction resulted in a strong increase <strong>of</strong> the<br />
reaction rate under the same experimental conditions (1.5 wt% KOH as catalyst and<br />
temperature <strong>of</strong> 60°C). Such microwave-assisted system allowed us to obtain the same<br />
ethyl-ester yield after only 10 min <strong>of</strong> reaction. Our results indicated that microwave heating<br />
can effectively reduce the reaction time probably due to a change in Arrhenius preexponential<br />
factor.<br />
We next investigated the microwave-assisted glycerol etherification to selectively produce<br />
short-chain oligomers in the presence <strong>of</strong> homogeneous bases at temperatures ranging<br />
from 200 to 260°C. While a complete glycerol conversion was observed after 6h <strong>of</strong><br />
reaction under conventional heating, the same conversion was attained after only 1h with<br />
the microwave-assisted system. More surprisingly, diglycerol was mainly obtained with a<br />
yield as high as 90 % under such reaction conditions, whereas a complex mixture <strong>of</strong><br />
polyglycerols was formed under conventional heating with a diglycerols yield less than<br />
50%.<br />
In summary, we have shown that the microwave-assisted production <strong>of</strong> ethylesters derived<br />
from castor oil was more easily achieved with shorter times compared to conventional<br />
methods. A similar trend was observed for the formation <strong>of</strong> diglycerol where a fairly<br />
unexpected yield <strong>of</strong> 90 % was obtained. Future studies will focus both on a fundamental<br />
approach <strong>of</strong> the alcohol activation and on the scaling up <strong>of</strong> the microwave-assisted esters<br />
or ethers production.<br />
Acknowledgement<br />
The authors acknowledge CODI - University <strong>of</strong> Antioquia for financing the project,<br />
Colciencias for the Ph.D. scholarship <strong>of</strong> G.H. and ‘VALAGRO Carbone Renouvelable<br />
Poitou-Charentes’ for fruitful discussion.<br />
52
L34<br />
Synthesis and application <strong>of</strong> cyclic carbonates <strong>of</strong> fatty acid esters<br />
Benjamin Schäffner 1 , Matthias Blug 1 , Daniela Kruse 1 , Benjamin Woldt 1 , Mykola Polyakov 2 ,<br />
Angela Köckritz 2 , Andreas Martin 2 , Sebastian Jung 3 , David Agar 3 , Bettina Rüngeler 4 ,<br />
Andreas Pfennig 5 , Karsten Müller 5 , Wolfgang Arlt 5 ,<br />
1<br />
Evonik Industries AG, Germany; 2 Leibniz-Institute for Catalysis e.V., Rostock, Germany;<br />
3 TU Dortmund, Dortmund, Germany; 4 RWTH Aachen, Aachen, Germany; 5 TU Graz,<br />
Graz, Austria; 6 University <strong>of</strong> Erlangen- Nuremberg, Erlangen, Germany<br />
benjamin.schaeffner@evonik.com<br />
A cascaded method for the development <strong>of</strong> new processes using carbon dioxide has been<br />
developed in the public-funded project a H 2 ECO 2 coordinated by the Science-to-Business<br />
Center Eco² <strong>of</strong> Creavis, the strategic research and development unit <strong>of</strong> Evonik. The<br />
procedure includes a thermodynamic, ecological and economic analysis as well as the<br />
evaluation <strong>of</strong> the catalytic and process feasibility. Industrial relevant target molecules have<br />
been identified with a great CO 2 -saving potential. Suitable catalysts and a synthetic route<br />
have been designed and a Life-Cycle-Analysis for the new product has been completed<br />
(Scheme 1).<br />
Scheme 1: Life-Cycle <strong>of</strong> a new product in comparison to the benchmark.<br />
The combination <strong>of</strong> fatty acid derivatives and CO 2 as building block can yield an interesting<br />
class <strong>of</strong> compounds known as fatty acid carbonates. The use <strong>of</strong> CO 2 as chemical building<br />
block has the chance to mitigate CO 2 -emissions from power plants and large industrial<br />
sites. The consortium established a robust route to synthesize cyclic carbonates from fatty<br />
acid epoxides in order to test their potential in applications (Scheme 2). Furthermore, a<br />
Life-Cycle-Analysis was performed with an established benchmark to compare the<br />
environmental footprint and CO 2 -emissions.<br />
O<br />
R<br />
O<br />
O<br />
O<br />
O<br />
[Catalyst]<br />
, CO 2<br />
O<br />
R<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
O<br />
Scheme 2: Synthesis <strong>of</strong> cyclic carbonates <strong>of</strong> epoxidized fatty acid esters and CO 2 .<br />
a This project is funded by the German state <strong>of</strong> North Rhine-Westphalia (Ministry for<br />
innovation, science and research) and co-financed by the EU (European Regional<br />
Development Fund).<br />
53
<strong>Abstracts</strong><br />
Part 2: Posters<br />
55
P1<br />
Green synthesis <strong>of</strong> biolubricants from castor oil and higher chain<br />
alcohols<br />
Chandu S. Madankar, Subhalaxmi Pradhan, S.N. Naik,<br />
Indian Institute <strong>of</strong> Technology, Delhi, India<br />
chandumadankar@gmail.com<br />
Renewable raw materials are playing important role in developing environmentally<br />
sustainable products. The consumption <strong>of</strong> oils and fats from vegetable and animal origin is<br />
increasing, as the trend is moving towards more eco friendly products. The use <strong>of</strong><br />
environmentally acceptable vegetable oil-based product as lubricants has many<br />
advantages, as they are nontoxic, biodegradable, derived from renewable resources, and<br />
have a reasonable cost when compared to other synthetic fluids. Castor oil content about<br />
87% <strong>of</strong> ricinoleic acid which is a hydroxy acid and having high viscosity as compared to<br />
other vegetable oils, thus the use <strong>of</strong> castor oil in lubricants is more prevalent. We have<br />
made an attempt to develop a green process for the production <strong>of</strong> bio lubricants from<br />
castor oil. The process includes the enzymatic transesterification <strong>of</strong> castor oil with higher<br />
chain alcohols in solvent and solvent free medium led to the production <strong>of</strong> fatty acid alkyl<br />
esters, which can be used as biolubricants. In this study, the reaction parameters<br />
investigated were the reaction time, temperature, enzyme loading, mixing speed and molar<br />
ratio (alcohol to triglycerides), and their effect on the alkyl esters formation. The lubricity <strong>of</strong><br />
the alkyl esters were measured using High frequency reciprocating rig (HFRR).<br />
56
P2<br />
Potassium Fluoride Impregnated CaO/NiO: An Efficient Heterogeneous<br />
Catalyst for Transesterification <strong>of</strong> Triglycerides<br />
Mandeep Kaur, Amjad Ali, Thapar University, Patiala India<br />
mandeepthapar@gmail.com<br />
Potassium impregnated CaO/NiO has been prepared by wet impregnation method in nano<br />
particle form as supported by powder X–ray diffraction, Scanning electron microscopy<br />
(SEM) and Transmission electron microscopy (TEM). BET surface area measurements<br />
and Hammett indicator studies have done in order to establish the effect <strong>of</strong> potassium<br />
impregnation on catalyst structure, particle size, surface morphology and basic strength.<br />
CaO/NiO impregnated with 20 wt% potassium was used as solid catalyst for the<br />
transesterification <strong>of</strong> different triglyceride (Fresh cottonseed oil, Waste cottonseed oil,<br />
Karanja oil, Jatropha oil, Soybean oil) having free fatty acid contents in the range <strong>of</strong> 0.32–<br />
8.3 wt %. The variables used for the transesterification were KF impregnated on CaO/NiO,<br />
catalyst concentration, reaction temperature, methanol to oil molar ratio, reaction time and<br />
free fatty acid content. Reaction parameters have been optimized to achieve the least<br />
reaction period for the completion <strong>of</strong> the reaction. Complete transesterification <strong>of</strong> waste<br />
cotton seed oil with methanol required 4 h in the presence <strong>of</strong> KF impregnated CaO/NiO<br />
nano catalyst at 65 ºC with 15:1 methanol to oil and 5 wt% (catalyst/oil) <strong>of</strong> catalyst.<br />
57
P3<br />
In-situ monitoring and induction time measurements during melt<br />
crystallization <strong>of</strong> plant based fatty acid mixtures in V-form reactor<br />
Sunanda Dasgupta, Peter Ay, Chair <strong>of</strong> Mineral Processing, Processing <strong>of</strong> Biogenous<br />
Resources, Brandenburg University <strong>of</strong> Technology, Germany<br />
dasgupta@tu-cottbus.de<br />
Enriched plant based unsaturated fatty acid mixtures are increasingly finding applications<br />
in various fields like those <strong>of</strong> production <strong>of</strong> bio-fuels and polymerization <strong>of</strong> epoxy resins. In<br />
the case <strong>of</strong> production <strong>of</strong> epoxy resins, they are highly advantageous due to the presence<br />
<strong>of</strong> multiple double bonds in the fatty acids which provide opportunities for cross linking by<br />
substitution. On the other hand, bio-fuels need raw materials with very low crystallization<br />
temperatures. This special property can also be attributed to these enriched unsaturated<br />
fractions due to their weak inter-molecular interactions owing to the kink in their structures.<br />
Melt crystallization has long been established as an optimal method for purification and<br />
enrichment <strong>of</strong> fractions from mixtures [1,2]. Previous studies have shown promising results<br />
with regard to enrichment <strong>of</strong> unsaturated fractions by melt crystallization processes [1].<br />
Melt crystallization kinetics <strong>of</strong> two plant based poly-unsaturated fatty acid mixtures have<br />
been investigated in this study [3]. A high oleic and a high linoleic fatty acid mixture were<br />
chosen for comparison purposes. A V-form reactor was developed for optimal in-situ<br />
analysis with the help <strong>of</strong> the focused beam reflectance measurement (FBRM®, Mettler<br />
Toledo Ltd., Switzerland) instrument [3]. Enhanced heat transfer especially to deal with the<br />
heat given out during crystallization was enabled through minimal volume <strong>of</strong> sample,<br />
optimized mixing and the special shape <strong>of</strong> the reactor. Important parameters like induction<br />
time, mixing speed, etc have been determined and compared as functions <strong>of</strong> degree <strong>of</strong><br />
supercooling and composition <strong>of</strong> PUFA mixtures. In accordance to theory, the induction<br />
times in both the cases decreased with increasing supercooling and mixer speed. On the<br />
other hand, the high linoleic fatty acid mixture required much higher supercooling (4.4K to<br />
5.4K) than the high oleic mixture (2.2K to 3.2K) for favorable induction times.<br />
References<br />
[1] S. Dasgupta, N. Dreiack, P. Ay, presented at the 5th Workshop on Fats and Oils as<br />
Renewable Feedstock for the Chemical Industry (Eds: J.O. Metzger, M.A.R. Meier),<br />
Karlsruhe 2012<br />
[2] G.F. Arkenbout, Melt Crystallization Technology, Technomic Publishing Company Inc.,<br />
Pennsylvania 1995<br />
[3] S. Xu, Master thesis, Chair <strong>of</strong> Mineral Processing, Processing <strong>of</strong> Biogenous Resources,<br />
Brandenburg University <strong>of</strong> Technology, Cottbus 2010<br />
58
P4<br />
Biomass conversion: Preparation <strong>of</strong> glycerol carbonate esters by<br />
esterification with hybrid Nafion-silica catalyst<br />
Sergio Martínez Silvestre, Maria José Climent Olmedo, Avelino Corma Canós, Sara Iborra<br />
Chornet, Instituto de Tecnología Química, Valencia, Spain<br />
sermars4@itq.upv.es<br />
Glycerol carbonate esters (GCEs) which are valuable biomass derivative compounds have<br />
been prepared by direct esterification starting from glycerol carbonate and long organic<br />
acids with different chain length in absence <strong>of</strong> solvent and using acid organic resins,<br />
zeolites and hybrid organic-inorganic acid catalysts as heterogeneous catalysts. The best<br />
results in terms <strong>of</strong> activity and selectivity to glycerol carbonate esters have been obtained<br />
using a Nafion-silica composite. A full reaction scheme has been established and it has<br />
been found that an undesired competing reaction is the generation <strong>of</strong> glycerol and esters<br />
derived from a secondary hydrolysis <strong>of</strong> the endocyclic ester group due to water formed<br />
during the esterification reaction. The influence <strong>of</strong> temperature, substrates ratio, catalyst to<br />
substrate ratio and use <strong>of</strong> solvent has been studied and, under optimized reaction<br />
conditions, it is possible to achieve 95% selectivity to the desired product at 98%<br />
conversion. It was found that reaction rate decreased as the number <strong>of</strong> carbons in the<br />
linear alkyl chain <strong>of</strong> the carboxylic acid increases for both p-toluenesulfonic acid and<br />
Nafion SAC-13. Fitting experimental data to a mechanistically based kinetic model, the<br />
reaction kinetic parameters for Nafion SAC-13 catalysis were determined and compared<br />
when reacting different carboxylic acids. The enthalpy <strong>of</strong> adsorption, activation energy and<br />
entropy <strong>of</strong> the surface reaction indicate that the lower reactivity <strong>of</strong> the carboxylic acid in<br />
this reaction when increasing the chain length kinetic study is supported by inductive as<br />
well as entropic effects.<br />
59
P5<br />
Time-resolved characterization <strong>of</strong> aging products from fatty acid methyl<br />
esters<br />
Stephanie Flitsch, Sigurd Schober, Martin Mittelbach,<br />
Institute <strong>of</strong> Chemistry, University <strong>of</strong> Graz; Graz, Austria<br />
stephanie.flitsch@uni-graz.at<br />
Fatty acid methyl esters (FAME) are the main components <strong>of</strong> biodiesel. They are subject<br />
to chemical aging and play a major role in fuel aging processes <strong>of</strong> biodiesel and<br />
diesel/biodiesel blends. The occurrence <strong>of</strong> FAME aging products in standard diesel<br />
engines may result in damage to fuel-carrying or engine parts. While numerous sum<br />
parameters are available to characterize fuel aging properties, very little research has<br />
been done on the analysis <strong>of</strong> specific aging products.<br />
The aim <strong>of</strong> this work is to develop a deeper understanding <strong>of</strong> the processes <strong>of</strong> FAME<br />
aging.<br />
FAMEs were aged by applying high temperatures (110°C) and a constant stream <strong>of</strong> air via<br />
a Rancimat device. FAME hydroperoxides were identified and characterized as the<br />
primary aging products. Secondary aging products include short-chain fatty acids,<br />
aldehydes, alcohols, and epoxides.<br />
The formation <strong>of</strong> aging products is monitored during time-resolved measurements using<br />
gas chromatography-mass spectrometry (GC-MS) and ion exchange chromatography<br />
(IEC) [1]. Additionally, polymer formation is monitored via size-exclusion chromatography<br />
(SEC) [2]. The concentration <strong>of</strong> hydroperoxides reaches its maximum shortly before the<br />
investigated FAME reaches its IP. An increase in the formation <strong>of</strong> secondary aging<br />
products is observed after the investigated FAME reaches its IP.<br />
[1] Morales A, Dobarganes C, Márquez-Ruiz G, Velasco J, 2010: Quantitation <strong>of</strong><br />
Hydroperoxy-, Keto- and Hydroxy-Dienes During Oxidation <strong>of</strong> FAMEs from High-Linoleic<br />
and High-Oleic Sunflower Oils, Journal <strong>of</strong> the American Oil Chemists Society, 87, 1271-<br />
1279<br />
[2] Márquez-Ruiz G, Holgado F, García-Martínez MC, Dobarganes MC, 2007: A Direct and<br />
Fast Method to Monitor Lipid Oxidation Progress in Model Fatty Acid Methyl Esters by<br />
High-Performance Size-Exclusion Chromatography, Journal <strong>of</strong> Chromatography A, 1165,<br />
122-127<br />
60
P6<br />
Solvent Assisted Hydraulic Pressing <strong>of</strong> Dehulled Rubber Seeds<br />
Muhammad Yusuf Abduh, Erna Subroto, Robert Manurung, Hero Jan Heeres,<br />
Universitty <strong>of</strong> Groningen, Groningen, Netherlands<br />
p262868@rug.nl<br />
Rubber seed oil (RSO) has potential to be used for biodiesel synthesis [1, 2]. We have<br />
carried out experimental studies on the solvent assisted hydraulic pressing (SAHP) <strong>of</strong><br />
rubber seeds with the objective to enhance oil recovery yields. Ethanol was used as the<br />
solvent as it is available from renewable resources, non-toxic and poses less handling<br />
risks than hexane [3]. Dehulled rubber seeds were pressed in a laboratory scale hydraulic<br />
pressing machine. The effect <strong>of</strong> seed moisture content (0-6 % w.b.), temperature (35-105<br />
oC), pressure (15- 25 MPa) and solvent to seed ratio (0.07- 0.21 % (v/w)) on the oil<br />
recovery was investigated. An optimum oil recovery <strong>of</strong> 74 % d.b. was obtained when 2 %<br />
w.b. dehulled rubber seeds were pressed in the presence <strong>of</strong> ethanol at 20 MPa, 75oC and<br />
10 min pressing time, which is about 8% better than in the absence <strong>of</strong> ethanol. The<br />
experimental dataset was modelled using two approaches, viz i) a regression model using<br />
Response Surface Methodology (RSM) and ii) a fundamental model developed by Shirato<br />
[4]. Both models give a good description <strong>of</strong> the effects <strong>of</strong> process conditions on oil yields.<br />
The moisture content <strong>of</strong> the seeds and temperature has the most significant effect on the<br />
oil recovery followed by pressure and solvent to seed ratio (Figure 1).<br />
Figure 1 Effect <strong>of</strong> moisture content and temperature on the oil recovery <strong>of</strong> SAHP <strong>of</strong><br />
dehulled rubber seeds as modelled by RSM<br />
In conclusion, we have shown that ethanol assisted hydraulic pressing has a clear<br />
beneficial effect on the oil recovery oil yield for dehulled rubber seeds.<br />
[1] Ikwuagwu, O. E.; Ononogbu, I.C.; Njolu, O.U., Industrial Crops Products, 12 (2000),<br />
57–62.<br />
[2] Morshed, M.; Ferdous, K.; Maksudur, R.K.; Mazumder, M.S.I.; Islam, M.A., Uddin, Md.<br />
T., Fuel, 90 (2011), 2981–2986.<br />
[3] Ferreira-Dias, S.; Valente, D.G.; Abreu, J.M.F., Grasas y aceites 54 (2003), 378–383.<br />
[4] Shirato, M.; Murase, T.; Iwata, M.; Nakatsuka, N, Chemical Engin. Sci. 41 (1986),<br />
3213–3216.<br />
61
P7<br />
Hydrotreating <strong>of</strong> Non-Food Fat and Oil Derivatives for the Production <strong>of</strong><br />
Bi<strong>of</strong>uels<br />
Alexander F. H. Studentschnig, Sigurd Schober, Martin Mittelbach,<br />
Institute <strong>of</strong> organic/bioorganic Chemistry, Karl-Franzens University Graz, Graz,, Austria<br />
alexander.studentschnig@uni-graz.at<br />
Fatty acid methyl esters are well established alternative bi<strong>of</strong>uels and have been<br />
successfully used as neat diesel fuel or as blend with fossil fuels around the world.<br />
However, due to limited stability and an oxygen content <strong>of</strong> about 10 %, the use in blends is<br />
limited by 7 % (vol/vol) due to European specifications. Hydrogenation <strong>of</strong> vegetable oils in<br />
combination with deoxygenation, decarbonylation and decarboxylation could lead to<br />
hydrocarbons, which could be used as so-called drop-in fuels with similar properties like<br />
fossil Diesel fuel or kerosene.<br />
Hydrotreating is used in conventional oil refineries to remove sulfur, nitrogen and metals<br />
from petroleum-derived feedstocks. Also high quality diesel fuel can be produced through<br />
this process [1]. Although hydrogenated vegetable oils have already been commercialized<br />
as so-called Next-BTL [2] or UOP’s Green DieselTM and Green Jet fuelTM<br />
[3] not much is known about the use <strong>of</strong> non-food feedstocks like waste vegetable oils,<br />
animal fat or fatty acids from<br />
oil refining.<br />
Fatty acid methyl esters from different non-food sources were successfully converted into<br />
n-alkanes in a batch reactor under hydrotreating conditions. Different formulations <strong>of</strong> selfprepared<br />
NiMo/Al2O3 were used as catalysts and the reaction kinetics was studied for<br />
each<br />
<strong>of</strong> the feedstocks at 360 and 380°C at a constant initial hydrogen pressure <strong>of</strong> 90<br />
bars,samples were taken periodically. These samples were analyzed for their composition<br />
by GC-MS. It could be found out that there are slight differences in turnover depending on<br />
the characteristics <strong>of</strong> the feedstock that seem to diminish by increasing the reaction<br />
temperature. The obtained products were tested on certain fuel properties such as the<br />
distillation range by simulated distillation via gas chromatography, cold flow properties and<br />
other general fuel parameters. As the main components <strong>of</strong> these synthetic hydrocarbon<br />
mixtures are n-alkanes in the diesel boiling range, blending with diesel fuel can easily be<br />
done.<br />
[1] G.W. Huber et al., Applied Catalysis A: General 329 (2007) 120–129<br />
[2] Neste Oil, http://www.nesteoil.com/, (accessed 01/2013)<br />
[3] Honeywell UOP, http://www.uop.com/, (accessed 01/2013)<br />
62
P8<br />
Enhancing the Acyltransferase Activity <strong>of</strong> Candida antarctica Lipase A<br />
Janett Müller, 1 Henrike Brundiek, 2 Birte Fredrich, 1 Uwe T. Bornscheuer, 1<br />
1 University <strong>of</strong> Greifswald, Greifswald, Germany; 2 Enzymicals AG, Greifswald, Germany<br />
janett.mueller@uni-greifswald.de<br />
Fatty acid esters are important compounds in different fields <strong>of</strong> application. Fatty acid<br />
methyl esters can be used as biodiesel and are an alternative to common diesel fuel.<br />
Moreover different fatty acid esters e. g. methyl laurate and ethyl laurate can be used as<br />
flavoring and fragrance compounds in the cosmetic industries.<br />
The synthesis <strong>of</strong> these compounds is <strong>of</strong>ten achieved by the use <strong>of</strong> lipases in water-free or<br />
low-water transesterification reactions where common oils are used as substrates.[1] But<br />
some lipases like the Candida antarctica lipase A (CAL-A) also possess an acyltransferase<br />
activity that enables the synthesis <strong>of</strong> fatty acid esters even in the presence <strong>of</strong> water.<br />
Avoiding the necessity <strong>of</strong> a water-free system can be an important cost factor concerning<br />
the industrial applicability <strong>of</strong> a certain process. In addition to that the CAL-A exhibits some<br />
characteristics, e.g. its thermostability that is favorable for industrial application and the 3D<br />
structure <strong>of</strong> the enzyme is available, which is beneficial for protein engineering.[2]<br />
For an engineering <strong>of</strong> the acyltransferase activity <strong>of</strong> CAL-A, the enzyme expression was<br />
established in E. coli and in Pichia pastoris.[3] The expression in E. coli is possible in<br />
deepwell plates. Thus larger mutant libraries can be screened. For such a screening<br />
different high-throughput assays are possible: on one hand the pH-shift caused by fatty<br />
acid consumption can be detected, on the other hand the consumption <strong>of</strong> alcohol can be<br />
measured by establishing an enzyme cascade that converts the alcohol further for<br />
example with an alcohol dehydrogenase or an oxidase.<br />
[1] Gog, A.; Roman M.; Toșa M.; Paizs C.; Irimie F. D. (2012); Biodiesel production using<br />
enzymatic transesterification - Current state and perspectives; Renew Energ 39: 10-16<br />
[2] Ericsson D.J.; Kasrayan A.; Johansson P.; Bergfors T.; Sandströn A. G.; Bäckvall J.-E.<br />
and Mowbray S. L. (2008); X-ray structure <strong>of</strong> Candida antarctica Lipase A shows a novel<br />
lid structure and a likely mod <strong>of</strong> interfacial activation; J. Mol. Biol. 376: 109-119<br />
[3] Brundiek, H.B., Evitt, A.S., Kourist, R., Bornscheuer U.T. (2011); Creation <strong>of</strong> a lipase<br />
highly selective for trans fatty acids by protein engineering; Angew. Chem. Int. Ed. 51:<br />
412-414.<br />
63
P9<br />
TEMPERATURE AND COMPOSITION DEPENDENCE OF DENSITY FOR<br />
SOYBEAN OIL, EPOXIDIZED SOYBEAN OIL AND ACETIC ACID BINARY<br />
MIXTURES<br />
64<br />
Milovan Jankovic 1 , Olga Govedarica 1 , Snezana Sinadinovic-Fiser 1 , Vesna Rafajlovska 2<br />
1 Faculty <strong>of</strong> Technology, University <strong>of</strong> Novi Sad, Serbia; 2 Faculty <strong>of</strong> Technology and<br />
Metallurgy, SS Cyril and Methodious University in Skopje, Macedonia<br />
ssfiser@uns.ac.rs<br />
Epoxidized soybean oil is biodegradable replacement for phthalates used in past as PVC<br />
stabilizers. By subjecting epoxidized soybean oil to ring opening reactions, high-funcionality<br />
vegetable oil-based materials applicable for resin preparation may be produced. Industrially,<br />
soybean oil is mainly epoxidized with peracetic acid formed in situ from acetic acid and hydrogen<br />
peroxide in the presence <strong>of</strong> an acid catalyst. Mineral acids, such as sulphuric acid, or acidic ion<br />
exchange resin are catalysts <strong>of</strong> choice. Such reaction system is two (oil-water) or three (oil-waterion<br />
exchange resin) phase, depending <strong>of</strong> applied catalyst. Two main reactions <strong>of</strong> peracetic acid<br />
and epoxy ring formation occur, as well as several side reactions <strong>of</strong> epoxy ring cleavage.<br />
Therefore, a rigorous kinetic model, necessary for process optimization, should include kinetic,<br />
thermodynamic and mass transfer parameters. Due to extensive number <strong>of</strong> the parameters, their<br />
simultaneous determination by fitting experimental data for the variation <strong>of</strong> components<br />
concentration with time is inconvenient and incorrect [1]. More appropriate should be to determine<br />
some <strong>of</strong> the parameters in separate experiments designed for investigation <strong>of</strong> particular<br />
phenomenon such as partitioning <strong>of</strong> components between phases [2]. For the multiphase<br />
epoxidation system, partition coefficient <strong>of</strong> acetic acid, KA, is the function <strong>of</strong> a liquid-liquid<br />
equilibrium constant for acetic acid, Kx,A, and molar volumes <strong>of</strong> compressed liquid for water and<br />
oil phase, vw and vo, respectively. Molar volume <strong>of</strong> compressed liquid is a ratio <strong>of</strong> molar mass, M,<br />
and a compressed liquid density, ρ.<br />
In this work, densities <strong>of</strong> pure components and their binary mixtures related to the oil phase <strong>of</strong> the<br />
reaction system <strong>of</strong> soybean oil epoxidation with peracetic acid formed in situ were measured and<br />
fitted with appropriate correlations found in literature. The aim was to determine temperature and<br />
composition dependence <strong>of</strong> the density. Measurements were done in the temperature range <strong>of</strong> 20<br />
to 800C and for mixture compositions that correspond to the component ratio in an industrial<br />
process. Spencer-Danner-Rackett [3] and COSTALD [4] correlations and Amagat`s law for<br />
calculation <strong>of</strong> molar volume <strong>of</strong> saturated liquid, as well as Yen-Woods [5] , Nasrifar-Moshfeghian<br />
[6], simplified Nasrifar-Moshfeghian [7] and Iglesias-Silva-Hall [8] correlations for saturated liquid<br />
density, were used. Tait equation is further applied to obtain corresponding values <strong>of</strong> molar volume<br />
<strong>of</strong> compressed liquid. Fitting the experimental data by Marquardt algorithm, a critical temperature,<br />
critical pressure, acentric factor and critical compressibility factor for soybean oil, epoxidized<br />
soybean oil and acetic acid for each applied correlation were calculated. The best fit model, with an<br />
average relative error <strong>of</strong> 0.59%, was found to be Spencer-Danner modification <strong>of</strong> Rackett equation.<br />
Acknowledgment: This work is part <strong>of</strong> the Project #III 45022 supported by the Ministry <strong>of</strong> Education<br />
and Science <strong>of</strong> the R. Serbia. The authors thank the DAAD and INFU, FR. Germany, for<br />
instrument donations.<br />
References:<br />
[1] M. Janković, S. Sinadinović-Fišer, M. Lamshoeft, J. Am. Oil Chem. Soc. (2010) 87:591-600<br />
[2] S. Sinadinović-Fišer, M. Janković, J. Am. Oil Chem. Soc. (2007) 84:669-674<br />
[3] C.F. Spencer, R.P. Danner, Chem. Eng. Data (1973) 18:230-234<br />
[4] R.W.Hankinson, G.H. Thompson, AIChE J. (1979) 26:653-663<br />
[5] L.C. Yen, S.S. Woods, AIChE J. (1966) 12:95-99<br />
[6] Kh. Nasrifar, M. Moshfeghian, Fluid Phase Equilib. (1999) 158-160:437-445<br />
[7] A. Mchaweh, A. Alsaygh, Kh. Nasrifar, M. Moshfeghian, Fluid Phase Equilib. (2004) 224:157-<br />
167<br />
[8] G.A. Iglesias-Silva, K.R. Hall, Fluid Phase Equilib. (1997) 131:97-105
P10<br />
Renewable Co-Polymers Derived from Limonene and Fatty Acid<br />
Derivatives<br />
Maulidan Firdaus, Michael A. R. Meier, Institute <strong>of</strong> Organic Chemistry, Karlsruhe<br />
Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
maulidan.firdaus@student.kit.edu<br />
The limited availability <strong>of</strong> petroleum resources and their escalating prices has led to an<br />
increase interest in the development <strong>of</strong> new platform chemicals from renewable resources.<br />
From the standpoint <strong>of</strong> cost and availability, fatty acid derivatives and (R)-(+)-limonene are<br />
among valuable renewable raw materials <strong>of</strong> great promise for polymer synthesis. Thus, we<br />
present a versatile and effective way to synthesize renewable diolefin and dithiols derived<br />
from (R)-(+)-limonene and/or fatty acid derivatives via thiol-ene addition. The monomers<br />
thus obtained have been characterized and their behavior in thermal or photochemical<br />
thiol-ene polyaddition have been investigated. Thus, through different combinations, (R)-<br />
(+)-limonene and fatty acid derivatives copolymers were prepared and their structurethermal<br />
property relationships were studied. GPC results and intensive DSC analysis <strong>of</strong><br />
the resulting polymers revealed that renewable polysulfides from amorphous to highmelting<br />
crystalline polymers with molecular weights up to 31.8 kDa can be obtained. In<br />
addition, polysulfones were also prepared by oxidation <strong>of</strong> corresponding polysulfides with<br />
hydrogen peroxide solution. DSC analysis demonstrated an increase in thermal properties<br />
when the polysulfides are oxidized into polysulfones. Overall, the combination <strong>of</strong> (R)-(+)-<br />
limonene and fatty acid derived monomers might open an entry to new polymers derived<br />
from these renewable resources.<br />
65
P11<br />
BIPHASIC KINETIC MODEL OF IN SITU EPOXIDATION OF CASTOR OIL<br />
WITH PERACETIC ACID<br />
Milovan Jankovic, Snezana Sinadinovic-Fiser, Olga Govedarica,<br />
Faculty <strong>of</strong> Technology, University <strong>of</strong> Novi Sad, Serbia<br />
oborota@uns.ac.rs<br />
Castor oil is a natural polyol which has in its fatty acid composition about 90% <strong>of</strong> monounsaturated<br />
hydroxy acid i.e. ricinoleic acid (12-hydroxy-9-octadecenoic acid). This renewable resource can be<br />
used for polyurethane production. However, more crosslinked polyurethane network may be<br />
obtained by introducing additional hydroxy groups in fatty acid chains <strong>of</strong> castor oil triglycerides.<br />
That can be achieved via epoxidation <strong>of</strong> double bonds, followed by transformation <strong>of</strong> epoxy groups<br />
to hydroxy groups.<br />
In large scale production <strong>of</strong> epoxidized vegetable oils common oxidizing agent is percarboxylic<br />
acid, such as performic or peracetic acid. It is usually obtained in situ through the acid catalyzed<br />
reaction <strong>of</strong> the corresponding organic acid with hydrogen peroxide. Soluble mineral acid, usually<br />
sulphuric acid, or acidic cation exchange resin, is commonly used as catalyst for this reaction [1].<br />
Besides the main reactions <strong>of</strong> percarboxylic acid and the epoxy ring formation, side reactions <strong>of</strong><br />
epoxy ring cleavage also occur [2]. Depending on the applied catalyst, the reaction system is either<br />
two- (oil-water) or three-phase (oil-water-ion exchange resin). Due to complexity <strong>of</strong> the reaction<br />
system, kinetic models that have been proposed are based on different simplifications [3].<br />
In this work the kinetics <strong>of</strong> the epoxidation <strong>of</strong> castor oil in benzene with peracetic acid generated in<br />
situ from acetic acid and hydrogen peroxide in the presence <strong>of</strong> an acidic cation exchange resin as<br />
the catalyst was studied. A pseudo-two phase kinetic model was developed. The side reaction <strong>of</strong><br />
epoxy ring with acetic acid involving the formation <strong>of</strong> hydroxyl acetate in addition to reactions <strong>of</strong> the<br />
formation <strong>of</strong> peracid and epoxy groups was considered. Approximate modeling <strong>of</strong> the peracetic<br />
acid formation, assuming that it occurs at the surface <strong>of</strong> the ion exchange resin, was based on<br />
Langmuir-Hinshelwood-Hougen-Watson (LHHW) and Rideal-Eley (RE) postulates. Depending on<br />
which reactants/products are adsorbed/desorbed on active catalyst sites and which step <strong>of</strong> this<br />
heterogeneous catalytic reaction determines the overall reaction rate, 18 models were established.<br />
Temperature dependency <strong>of</strong> the reaction rate coefficients ki and sorption equilibrium constants KS<br />
were expressed by reparameterized Arrhenius equation. The model parameters, i.e. constants <strong>of</strong><br />
the Arrhenius equation were determined by fitting experimental data for epoxidations run under<br />
different reaction conditions using the Marquardt method. After model discrimination the best fit<br />
model was accepted. It assumes that acetic acid, hydrogen peroxide, peracetic acid and water are<br />
chemisorbed on the active catalytic sites without dissociation and that acetic acid adsorption is the<br />
overall rate-determining step. Good agreement between the calculated and experimental values<br />
indicated the suitability <strong>of</strong> the proposed kinetic model.<br />
Acknowledgment: This work is part <strong>of</strong> the Project #III 45022 supported by the Ministry <strong>of</strong> Education<br />
and Science <strong>of</strong> the R. Serbia. The authors thank the DAAD and INFU, FR Germany, for instrument<br />
donations.<br />
References:<br />
[1] B.M. Abdullah, J. Salimon (2010) Epoxidation <strong>of</strong> vegetable oils and fatty acids: catalysts,<br />
methods and advantages, J. Applied Sci. 10:1545-1553<br />
[2] A. Campanella, M.A. Baltanás (2006) Degradation <strong>of</strong> the oxirane ring <strong>of</strong> epoxidized vegetable<br />
oils in liquid-liquid heterogeneous reaction systems, Chem. Eng. J. 118:141-152<br />
[3] S. Sinadinović-Fišer, M. Janković, O. Borota (2012) Epoxidation <strong>of</strong> castor oil with peracetic acid<br />
formed in situ in the presence <strong>of</strong> an ion exchange resin, Chem. Eng. Process. 62:106-113<br />
66
P12<br />
Thiol-yne Approach to Biobased Polyols: Polyurethane Synthesis and<br />
Surface Modification<br />
Cristina Lluch, Gerard Lligadas, Joan Carles Ronda, Marina Galià, Virginia Cádiz,<br />
Universitat Rovira i Virgili, Tarragona, Spain<br />
cristina.lluch@urv.cat<br />
Nowadays, the use <strong>of</strong> vegetable oils and their fatty acids for the synthesis <strong>of</strong> polymers<br />
represents an important contribution to sustainable development.1 In the last few years,<br />
click chemistry reactions in combination with renewable resources has attracted a lot <strong>of</strong><br />
interest in the field <strong>of</strong> Green Chemistry.<br />
Besides, the unceasingly demands <strong>of</strong> modern societies for new high performance<br />
materials should be translated in fostering higher versatile polymers. The design <strong>of</strong><br />
smarter polymers with broader application could be accomplished by introduction <strong>of</strong><br />
auxiliary functional groups onto the polymer backbone, which can be further modified ondemand.2<br />
Thiol-yne click chemistry has shown to be successful to obtain oligothioethers by UVinitiated<br />
polymerization <strong>of</strong> 10-undecynoic acid with dithiols.3 In this work, we aim at<br />
preparing oligothioethers from 10-undecynoic acid and its ester and hydroxyl derivatives<br />
(methyl 10-undecynoate and 10-undecynol) via a photoinitiated thiol-yne click chemistry<br />
approach using 3,6-dioxa-1,8-octanedithiol, as a dithiol. The combination <strong>of</strong> these<br />
monomers in different ratios yields brush-type polyols which have been used in the<br />
synthesis <strong>of</strong> polyurethanes with pendant acid and ester groups. This synthetic route<br />
provides the straightforward obtention <strong>of</strong> functional polyurethanes with no need <strong>of</strong> time and<br />
cost-consuming protection-deprotection steps.<br />
The surface <strong>of</strong> the resulting thermosets has been tailored via a mild and efficient postpolymerization<br />
modification allowing tuning the hydrophobic-hydrophilic properties <strong>of</strong> the<br />
final polymer. This postpolymerization reaction could be easily extended to a wide range <strong>of</strong><br />
components to provide new value-added characteristics to the polymer.<br />
1 Ronda J. C.; Lligadas, G; Galià, M; Cádiz, V. Eur. J. Lipid Sci. Technol., 2011, 113, 46–58.<br />
2 Fournier, D; De Geest B.G; Du Prez, F.E. Polymer, 2009, 50, 5362-5367.<br />
3 Türünç, O; Meier, M. A. R. J. Polym. Sci. Part A: Polym. Chem,. 2012, 50, 1689–1695.<br />
67
P13<br />
Heteropoly acids for conversion <strong>of</strong> renewable feedstocks<br />
Ali M. Alsalme, Abdulaziz A. Alghamdi,<br />
King Saud University, Riyadh, Saui-Arabia<br />
aalsalme@ksu.edu.sa<br />
Introduction<br />
Alternative fuels developed from renewable feedstocks have attracted much interest<br />
recently. Biodiesel is one <strong>of</strong> such alternative fuels produced from vegetable oils or animal<br />
fats. Commercial production <strong>of</strong> biodiesel employs homogeneous alkali catalysts. However,<br />
alkali catalysts, along with liquid acid catalysts have some limitation. Solid acid catalysts<br />
have strong potential to replace liquid acids, eliminating separation, corrosion and<br />
environmental problems.<br />
α-Pinene is another important renewable feedstock. It is isomerised to produce camphene<br />
and limonene, important intermediates and ingredients in cosmetics, food and<br />
pharmaceutical industries. The drawback <strong>of</strong> commercial catalyst (TiO2) is its low rate and<br />
poor selectivity.<br />
The aim <strong>of</strong> this work was to study homogeneous and heterogeneous catalysis by<br />
heteropoly acids (HPAs) for conversion <strong>of</strong> renewable feedstocks to fuel and chemicals.<br />
Results and Discussion<br />
The composites under study comprised H3PW12O40 (HPW) supported on Nb2O5, ZrO2<br />
and TiO2. Catalyst texture, state <strong>of</strong> HPW on the surface, catalyst crystallinity, nature and<br />
strength <strong>of</strong> acid sites were investigated using different techniques including nitrogen<br />
adsorption using the BET method, Fourier transform infrared spectroscopy (FT-IR), X-ray<br />
diffraction (XRD), 31P MAS NMR and differential scanning calorimetry (DSC) as well as<br />
isopropanol dehydration as a test reaction.<br />
HPAs were found to be active catalysts for the esterification <strong>of</strong> hexanoic acid and<br />
transesterification <strong>of</strong> ethyl propanoate and ethyl hexanoate with methanol in both<br />
homogeneous and heterogeneous liquid-phase systems. In homogeneous system, HPAs<br />
were much more active than H2SO4 in terms <strong>of</strong> turnover frequency (TOF). TOF for HPW<br />
supported on Nb2O5, ZrO2 and TiO2 was higher than that <strong>of</strong> the conventional solid acid<br />
catalysts such as Amberlyst-15, HY and H-Beta. However, these catalysts suffered from<br />
leaching and exhibited significant contribution <strong>of</strong> homogeneous catalysis by the leached<br />
HPA.<br />
-pinene over HPW supported on Nb2O5, ZrO2 and TiO2αIsomerisation <strong>of</strong> was carried out<br />
in the gas-phase at 200oC. The catalytic activity, selectivity and deactivation resistance <strong>of</strong><br />
these catalysts were compared with “standard” HPAs such as bulk HPW, CsPW and<br />
HPW/SiO2 and was found to be greatly dependent on the catalyst acidity. The catalysts<br />
possessing very strong Brønsted acid sites such as bulk HPW and CsPW suffered from<br />
intense deactivation. On the contrary, HPW supported on Nb2O5, ZrO2 and TiO2,<br />
possessing weaker acids, exhibited more stable as well as more selective performance in<br />
this reaction.<br />
68
P14<br />
Flexible polyurethane foams modified with selectively hydrogenated<br />
rapeseed oil<br />
Sylwia Dworakowska 1 , Dariusz Bogdal 1 , Federica Zaccheria 2 , Nicoletta Ravasio 2 ,<br />
1 Cracow University <strong>of</strong> Technology, Cracow, Poland; 2 Institute <strong>of</strong> Molecular Science and<br />
Technologies, National Research Council (CNR-ISTM), Milano, Italy<br />
sylwiadworakowska@gmail.com<br />
Nowadays, much attention is paid to the use <strong>of</strong> polyols derived from vegetable oils for the<br />
preparation <strong>of</strong> polyurethane foams due to both environmental as well as economical point<br />
<strong>of</strong> view [1]. Natural oils are valuable renewable raw materials, which can be widely used in<br />
synthesis and modification <strong>of</strong> polymers as an alternative to petrochemical sources [2].<br />
The aim <strong>of</strong> this study was to apply vegetable oils stabilized through a selective<br />
hydrogenation process [3] for their use in the preparation <strong>of</strong> polyols and therefore in the<br />
synthesis <strong>of</strong> polyurethane foams. Rapeseed oil-based polyols were synthesized using<br />
epoxidation followed by ring opening method (Fig. 1).<br />
Fig. 1. Synthesis <strong>of</strong> polyols from rapeseed oil through epoxidation and oxirane ring<br />
opening process. R” and R”’- residues <strong>of</strong> fatty acids.<br />
Flexible polyurethane foams were synthesized by substituting a portion <strong>of</strong> base polyether<br />
polyol with rapeseed oil-derived polyol. The influence <strong>of</strong> these modifications on the<br />
selected physico-chemical properties <strong>of</strong> synthesized foams was investigated.<br />
Selective hydrogenation represent a valuable tool for vegetable oils composition<br />
standardization. Moreover, the use <strong>of</strong> oils with a homogeneous composition and a very<br />
high content in C18:1 improves the final properties <strong>of</strong> the flexible foams making them more<br />
yellowing resistant due to the low level <strong>of</strong> unreacted double bonds [4].<br />
COST Action CM0903 UBIOCHEM is acknowledged for the support in the Short Term<br />
Scientific Missions <strong>of</strong> Sylwia Dworakowska and Federica Zaccheria.<br />
References<br />
1. Veenendaal B.: Polyurethanes Magazine International, 2007, 4(6) 352-359.<br />
2. Dworakowska S.; Bogdal D.; Prociak A.: Polymers, 2012, 4(3) 1462-1477.<br />
3. Zaccheria F.; Psaro R.; Ravasio N.; Bondioli P.: Eur. J. Lipid Sci. Technol., 2012, 114 24-30.<br />
4. Heidbreder A.; Gruetzmacher R.; Nagorny U.; Westfechtel A.: US2002/0161161 A1, 2002.<br />
69
P15<br />
Synthesis, purification and modification <strong>of</strong> abietic acid dimer, an<br />
interesting source <strong>of</strong> (co)monomers for the design <strong>of</strong> novel renewable<br />
polymers<br />
Audrey LLEVOT, Stephane CARLOTTI, Stephane GRELIER, Henri CRAMAIL,<br />
LCPO, PESSAC, France<br />
llevot@enscbp.fr<br />
As petroleum resources are decreasing and environmental concerns are growing, more<br />
attention is paid to the partial replacement <strong>of</strong> fossil resources by renewable ones. In the<br />
plastic industry, vegetable oils are considered as suitable alternative resources thanks to<br />
their availability and sustainability. However, the linear aliphatic structure <strong>of</strong> these<br />
monomers is an issue when polymers with high Tg, Tm are requested. The<br />
copolymerization <strong>of</strong> these vegetable-based monomers with cyclo-aliphatic resinic<br />
derivatives can be a solution to enhance the material rigidity.<br />
Rosin -or colophony- is mainly obtained by the distillation <strong>of</strong> a tall oil, a by-product <strong>of</strong> the<br />
Kraft pulp process, or by tapping living pine trees. It is composed <strong>of</strong> 10% <strong>of</strong> neutral<br />
compounds and 90% <strong>of</strong> isomeric organic acid mixtures, mainly abietic acid (40-60%). The<br />
production <strong>of</strong> rosin is more than 1 million metric ton per year and is commonly used in<br />
adhesives and inks.<br />
In this study, abietic acid has been first dimerized following the Sinclaire’s method. A<br />
mixture <strong>of</strong> abietic acid, dimers and trimers <strong>of</strong> abietic acid have been obtained from the<br />
solution. Conditions <strong>of</strong> separation <strong>of</strong> the compounds have been determined using HPLC.<br />
The adaptation <strong>of</strong> these conditions on a Flash chromatography apparatus allowed the<br />
isolation <strong>of</strong> the dimers. GC and NMR analyses have been performed before and after the<br />
separation. The richer fraction in dimers shows a purity <strong>of</strong> 92% by GC analyses.<br />
In a second step, the dimers have been esterified with different alcohols under mild<br />
conditions. Then several strategies <strong>of</strong> copolymerizations with fatty acids have been<br />
investigated. For instance, after esterifcation with undecenol, the diester dimer <strong>of</strong> abietic<br />
acid has been readily copolymerized with undecenyl undecenoate by ADMET (acyclic<br />
diene metathesis) yielding novel renewable polymers. The chemical structure and features<br />
<strong>of</strong> these polymers have been investigated by means <strong>of</strong> NMR, SEC, DSC and DMA.<br />
70
P16<br />
Rhodium-catalyzed hydr<strong>of</strong>ormylation <strong>of</strong> unsaturated fatty esters in<br />
aqueous media assisted by activated carbon<br />
Jérôme BOULANGER, Frédéric HAPIOT, Anne PONCHEL, Eric MONFLIER,<br />
UCCS Artois, Lens, France<br />
jerome.boulanger897@laposte.net<br />
Concerns about the environmental impact <strong>of</strong> chemical transformations prompted chemists<br />
to develop clean chemical processes using water as a solvent. Although appropriate for<br />
small partially water-soluble molecules, these processes do not allow for the<br />
transformation <strong>of</strong> hydrophobic substrates due to the mass transfer limitation between the<br />
aqueous and the organic phase. In this context, we show that activated carbons can be<br />
used as mass transfer additives to promote the rhodium-catalyzed hydr<strong>of</strong>ormylation <strong>of</strong><br />
methyl oleate and other unsaturated olefins. Due to its mesoporous and hydrophobic<br />
character, the Nuchar®WV-B activated carbon proved to be especially effective as mass<br />
transfer promoter. Actually, a significant increase in the conversion was observed.<br />
Additionally, more than 90% aldehydes were formed during the course <strong>of</strong> the reaction.<br />
When compared to other mass transfer promoters such as co-solvents or cyclodextrins,<br />
Nuchar®WV-B was by far the most efficient. Thus, the use <strong>of</strong> activated carbons appeared<br />
to be a suitable solution for the aqueous rhodium-catalyzed hydr<strong>of</strong>ormylation <strong>of</strong><br />
hydrophobic bio-sourced substrates.<br />
Reference: Jérôme Boulanger, Anne Ponchel, Hervé Bricout, Frédéric Hapiot, Eric<br />
Monflier, European Journal <strong>of</strong> Lipid Science and Technology, 2012, 114, 1439–1446.<br />
DOI:10.1002/ejlt.201200146<br />
71
P17<br />
Effect <strong>of</strong> some medicinal tea extracts on some oxidative parameters <strong>of</strong><br />
sesame oil<br />
Mehmet Musa Özcan 1 , Nurhan – Uslu 1 , Fahad Al Juhaimi 2 ,<br />
1 Selçuk University, Konya, Turkey; 2 King Saud University, Riyadh, Saui-Arabia<br />
mozcan@selcuk.edu.tr<br />
In this study, the antioxidant effect <strong>of</strong> some medicinal tea extract extracts at different<br />
concentrations (0.3 % and 0.5 %) on the oxidation parameters <strong>of</strong> sesame oil at 80 oC was<br />
determined. Butylated hydroxyanisole (BHA) was used as positive control in experiment.<br />
All extracts exhibited antioxidant activity compared to BHA upto 14 days. When antioxidant<br />
effect <strong>of</strong> extract concentrations were compared with BHA, the effect <strong>of</strong> 0.5 % extract<br />
concentration was more remarkable for sesame oil upto 14 days. All <strong>of</strong> seed extracts was<br />
effective at 80 oC in comparison with control. On the other hand, an important in both the<br />
peroxide and viscosity values during the experiment period increase was observed. It<br />
concluded that tea extract could be used as a oxidative inhibitor agent in oil and oil<br />
products.<br />
72
P18<br />
Self-metathesis <strong>of</strong> fatty acid methyl esters: Full conversion by choosing<br />
the appropriate plant oil<br />
Robert H<strong>of</strong>säß, Hatice Mutlu, Rowena E. Montenegro, Michael A. R. Meier<br />
Institute <strong>of</strong> Organic Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe<br />
robert.h<strong>of</strong>saess@googlemail.com<br />
New lines <strong>of</strong> research have been developed since the transformation <strong>of</strong> renewables has<br />
received major research interest both in academia and industry. In this domain, besides<br />
carbohydrates, fats and oils are the most commonly employed natural products. Especially<br />
the multifunctional character <strong>of</strong> triglycerides allows plant oils to be considered as valuable<br />
alternatives to fossil reserves. Considerable interest and attention has been focused on<br />
the transformation <strong>of</strong> oleochemicals into linear, long-chain α,ω-functionalized compounds<br />
in order to obtain the necessary monomers for the generation <strong>of</strong> diverse aliphatic poly-α,βunsaturated<br />
polymers. In this aspect, olefin-metathesis has the potential to enable a more<br />
efficient conversion <strong>of</strong> renewable and fossil feedstocks to difunctional alkenes.3 Thus,<br />
within this study, a sustainable and efficient route to diesters and there<strong>of</strong> derived<br />
polycondensates from plant oils was established. The high amount <strong>of</strong> polyunsaturated fatty<br />
acids in the investigated plant oils made an efficient self-metathesis reaction possible,<br />
since the volatile products cyclohexa-1,4-diene and hex-3-ene can be removed from the<br />
equilibrium reaction mixture. The removal <strong>of</strong> these compounds forced the reaction towards<br />
the desired α,ω-diester, leading to high yields (~80%). Also the scale up <strong>of</strong> the most<br />
promising fatty acid methyl ester mixture and catalyst combination was successful,<br />
allowing a production <strong>of</strong> the diester in higher amounts. Furthermore, efficient, quantitative<br />
reactions were used to obtain the saturated α,ω-diester and corresponding diol. The<br />
following polymerisation led to polyester 18,18 showing high molecular weight and high<br />
melting point. Last but not least, it should be emphasized that the by-products <strong>of</strong> the selfmetathesis<br />
reaction, cyclohexa-1,4-diene and hex-3-ene, are <strong>of</strong> great potential synthetic<br />
value.<br />
References<br />
P. Y. Dapsens, C. Mondelli and J. Perez-Ramirez, ACS Catal., 2012, 2, 1487-1499.<br />
U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O. Metzger and H. J. Schäfer, Angew<br />
Chem Int Ed., 2011, 50, 3854-3871.<br />
L. Montero de Espinosa and M. A. R. Meier, Eds. M. A. R. Meier, B. M. Weckhuysen, P. C.<br />
A. Bruijnincx, Springer, Heidelberg (Germany), 2012.<br />
H. Mutlu, R. H<strong>of</strong>säß, R. E. Montenegro and M. A. R. Meier, RSC Adv., 2013, DOI:<br />
10.1039/C3RA40330K.<br />
73
P19<br />
Synthesis and Characterization <strong>of</strong> New Biodegradable Poly(linoleic<br />
acid) / Poly(linolenic acid) Graft Copolymers<br />
Abdulkadir Allı 1 , Pınar Geçit 1 , Sema Allı 2 , Baki Hazer 2 ,<br />
1 Department <strong>of</strong> Chemistry, Düzce University, Düzce, Turkey; 2 Bülent Ecevit University,<br />
Turkey<br />
abdulkadiralli@duzce.edu.tr<br />
Plina / PLinl peroxides were obtained by the auto-oxidation <strong>of</strong> linoleic acid (Lina) and<br />
linolenic acid (Linl) respectively. The autooxidation <strong>of</strong> Lina and Linl under air at room<br />
temperature rendered waxy soluble polymeric peroxide, having soluble fraction more than<br />
98 weight percent (wt%) and containing up to 1.10-1.20 wt % <strong>of</strong> peroxide. Biodegradable<br />
poly (linoleic acid)-g-poly(ε-caprolactone) and poly (linolenic acid)-g-poly(ε-caprolactone)<br />
graft copolymers were synthesized via ring opening polymerization between autoxidized<br />
linoleic acid and linolenic acid peroxide initiators's carboxylic acid groups and ε-<br />
caprolactone monomer.<br />
In the second part <strong>of</strong> the study, one-step synthesis <strong>of</strong> graft copolymers by ring-opening<br />
polymerization and free radical polymerization by using polymeric linoleic acid peroxide<br />
and polymeric linoleic acid peroxide is studied. Graft copolymers having the structure <strong>of</strong><br />
poly (linoleic acid)-g-p-(N-isopropylacrylamide)-g-poly(D,L-lactid) were synthesized from<br />
polymeric linoleic acid peroxide possesing peroxide groups in the main chain by the<br />
combination <strong>of</strong> free radical polymerization <strong>of</strong> N-isopropylacrylamide and ring opening<br />
polymerization <strong>of</strong> D,L-lactid in one-step. The principal parameters such as monomer<br />
concentration, initiator concentration, and polymerization time that affect the one-step<br />
polymerization reaction were evaluated.<br />
The graft copolymers obtained were characterized by proton nuclear magnetic resonance<br />
(1H NMR), gel permeation chromatography (GPC), thermal gravimetric analysis (TGA)<br />
and differential scanning calorimetry (DSC) techniques. These characterization studies <strong>of</strong><br />
the obtained polymers indicate graft copolymers easily formed as a result <strong>of</strong> combination<br />
free radical polymerization and ring opening polymerization in one-step.<br />
74
P20<br />
Diversity in ADMET monomer synthesis via Passerini three component<br />
reactions with 10-undecenal as key building block<br />
Ansgar Sehlinger, Lucas Montero de Espinosa, Michael A. R. Meier, Institute <strong>of</strong> Organic<br />
Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
ansgar.sehlinger@gmail.com<br />
The use <strong>of</strong> plant oils, fatty acids, and there<strong>of</strong> derived platform chemicals in the synthesis <strong>of</strong><br />
polymers became increasingly important as a result <strong>of</strong> the limited availability <strong>of</strong> fossil oil<br />
resources.[1] Especially castor oil is a very interesting source <strong>of</strong> building blocks for organic<br />
synthesis. Pyrolysis <strong>of</strong> ricinoleic acid produces heptaldehyde and 10-undecenoic acid,<br />
which can be reduced to the corresponding 10-undecenal.[2] In this work, we focused on<br />
the use <strong>of</strong> 10-undecenal which was, besides acrylic acid and an isocyanide, the starting<br />
material for our monomer synthesis.<br />
The monomers were synthesized by a Passerini three component reaction (Passerini-<br />
3CR), which is a powerful tool to obtain structurally diverse molecules in a straightforward<br />
and atom economic fashion.[3] The one-pot synthesis <strong>of</strong> the mentioned starting materials<br />
leads to a library <strong>of</strong> asymmetric α,ω-dienes, containing an acrylate and a terminal double<br />
bond in the backbone. Such substrates show high cross-metathesis selectivity and thus<br />
polymerize strictly head-to-tail in an acylic diene metathesis (ADMET) polymerization.[4,5]<br />
This approach enables us to control the polymer structure and, in combination with the<br />
Passerini-3CR synthesis, to vary the functional groups <strong>of</strong> the repeating unit.<br />
Additionally, an amphiphilic block copolymer has been made by adding a PEG480-acrylate<br />
to the reaction mixture. This mon<strong>of</strong>unctional acrylate acts as a selective chain-stopper<br />
because it reacts only with one end <strong>of</strong> the polymer. Thus, we could show control over the<br />
molecular weight <strong>of</strong> the growing chain by using different ratios <strong>of</strong> monomer and chain<br />
stopper. Furthermore, the polymers thus obtained present acrylate end-groups, which<br />
allow for further post-modifications.<br />
[1] L. Montero de Espinosa, M. A. R. Meier, Eur. Polym. J. 2011, 47, 837.<br />
[2] H. Mutlu, M. A. R. Meier, Eur. J. Lipid Sci. Technol. 2010, 112, 10.<br />
[3] M. Passerini, Gazz. Chem. Ital. 1921, 51, 126.<br />
[4] A. K. Chatterjee, T. L. Choi, D. P. Sanders, R. H. Grubbs, J. Am. Chem. Soc. 2003,<br />
125, 11360.<br />
[5] L. Montero de Espinosa, M. A. R. Meier, Chem. Commun. 2011, 49, 1908.<br />
75
P21<br />
Malate production by Aspergillus orzyae<br />
Katrin Brzonkalik, Marina Bernhardt, Christoph Syldatk, Anke Neumann,<br />
KIT - Technical Biology, Karlsruhe, Germany<br />
katrin.brzonkalik@kit.edu<br />
L-malic acid is a C4 dicarboxylic organic acid and considered as a promising chemical<br />
building block. It can be applied as food preservative and acidulant, in rust removal<br />
because <strong>of</strong> its chelator properties and as polymerization starter unit due to its<br />
bifunctionality. Up to now it is produced chemically from crude oil via maleic anhydride.<br />
The mould Aspergillus oryzae produces malic acid in large quantities from glucose and<br />
other carbon sources. The microbial production <strong>of</strong> organic acids from renewable sources<br />
has the potential to be a sustainable alternative to petroleum and to reduce greenhouse<br />
gases as CO2 fixation is involved in microbial biosynthesis.<br />
In this study the production conditions were optimized in shaking flask experiments and a<br />
bioreactor fermentation was established to produce malic acid in large quantities. At 35°C<br />
up to 52 g/L malic acid were produced which corresponds to a molar yield <strong>of</strong> 1.13.<br />
76
P22<br />
Monitoring <strong>of</strong> Glyceride Synthesis in Multiphase System by ATR-Fourier<br />
Transform Infrared Spectroscopy<br />
Sören Baum 1 , Martin Schilling 2 , Fabien Cabirol 2 , Lutz Hilterhaus 1 , Andreas Liese 1 ,<br />
Institute <strong>of</strong> Technical Biocatalysis, TH Hamburg, Germany; 2 Evonik Industries AG<br />
soeren.baum@tuhh.de<br />
The assay <strong>of</strong> mono-, di-, and triglycerides in a multiphase system is <strong>of</strong> great importance in<br />
several industrial fields. Mixtures with a high content <strong>of</strong> monoglycerides with different fatty<br />
acid chain lengths are broadly used as emulsifiers and stabilizers for a variety <strong>of</strong> products<br />
in the food and cosmetics industry1. During synthesis <strong>of</strong> these components, it is <strong>of</strong><br />
desirable to achieve a high content <strong>of</strong> monoglycerides, whereby the di- or triglyceride<br />
content should be as low as possible. Therefore the analysis <strong>of</strong> the product composition<br />
and reaction selectivity plays an important role for the process control in the production<br />
process <strong>of</strong> glycerides.<br />
Conventional analytical methods for glycerides are gas chromatography (GC) or<br />
highpressure liquid chromatography2, which are <strong>of</strong> limited suitability for multiphase<br />
systems. This work demonstrates an in-situ differentiation between mono-, di- and<br />
triglycerides in a multiphase system by attenuated total reflectance (ATR) Fourier<br />
transform infrared spectroscopy. As a model system the enzymatic esterification <strong>of</strong><br />
glycerol with lauric acid was analyzed. The reaction was carried out in a bubble column<br />
reactor containing four phases (two liquid phases <strong>of</strong> glycerol and lauric acid, air as<br />
gaseous phase, and a heterogeneous catalyst as solid phase).<br />
For the study <strong>of</strong> this multicomponent system, a chemometric model was generated based<br />
on the calibration <strong>of</strong> the pure components only3. Deviations from the <strong>of</strong>fline data<br />
generated by GC were observed with respect to monoglyceride content during the course<br />
<strong>of</strong> the reaction. Therefore, the calibration was repeated applying detailed GC datasets <strong>of</strong><br />
real reaction samples. Internal as well as external validation (cross validated and test-set<br />
validated) showed significant lower deviations between <strong>of</strong>fline and online data. The<br />
quantities <strong>of</strong> lauric acid and 1-monolaurin, 2-monolaurin, 1,3-dilaurin, 1,2-dilaurin and<br />
trilaurin could be monitored over the course <strong>of</strong> the reaction. Thus, this technology has the<br />
potential to give accurate in situ results allowing its implementation as process control<br />
technology.<br />
(1) Hasenhuettl G.A, Hartel R.W, Food Emulsifiers and Their Application, 2nd ed.,<br />
Springer: New York, 2010.<br />
(2) Indrasti D, Man, Y. B. C, Chin S. T, Mustafa S, Hashim D.M, Manaf M.A, J. A. Oil<br />
Chem. Soc. 2010, 87(11), 1255–1262.<br />
(3) Müller J.J, Baum S, Hilterhaus L, Eckstein M, Thum O, Liese A, Simultaneous<br />
Determination <strong>of</strong> Mono-, Di- and Triglycerides in Multiphase Systems by Online FT-IR<br />
Spectroscopy. Anal. Chem., 2011, 83(24), 9321-9327.<br />
77
P23<br />
Pressure sensitive adhesives from renewable resources<br />
Wiebke Maassen, Norbert Willenbacher, Michael A. R. Meier, Institute <strong>of</strong> Organic<br />
Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
wiebke.maassen@kit.edu<br />
The so-called pressure-sensitive adhesives represent an important segment, which are<br />
used in different applications like labels, tapes and foils or special construction adhesives<br />
which are employed both for industrial and domestic purposes. However, these adhesives<br />
are almost exclusively petroleum-based synthetic products. Thus, currently ongoing<br />
research both in academia and industry is the shift from petrochemical adhesives to those<br />
incorporating natural and renewable materials. In line with this concept, the aim <strong>of</strong> the<br />
proposed projectis to evaluate the ability to produce such adhesives on the basis <strong>of</strong><br />
monomers which are synthesized using various fatty acids derived from vegetable oils.<br />
Appropriate polymers have been synthesized via standard radical polymerization<br />
procedures in bulk and solvent. It has been shown that the adhesion properties <strong>of</strong> the<br />
characterized homo-polymers are as good as equal polymers and co-polymers used in<br />
literature before[1]. Regarding a resources-protective and environmental friendly<br />
processing, the adhesives were manufactured successfully by means <strong>of</strong> miniemulsion<br />
polymerization as aqueous dispersions showing almost the same adhesive properties[2].<br />
Within the bulk and solvent based polymerization we were able to optimize the adhesive<br />
properties by using not only different bio based monomers for the polymer synthesis, but<br />
also by varying the degree <strong>of</strong> polymerization and cross-linking, as well as by using comonomers<br />
to get control over the visco-elastic properties leading to higher values in the<br />
storage and loss modulus. The visco-elastic and adhesive properties have been<br />
characterized using rheological[3] and mechanical standard measurements e.g. tack and<br />
peel tests[4]. For the first time it has been shown that by simple deprotection <strong>of</strong> the ester<br />
end group <strong>of</strong> the polymer side chain, one can improve the cohesion by generating<br />
hydrogen bonds in-between the bio based polymer.<br />
References<br />
[1] S.P. Bunker, R.P. Wool, J. Polym. Sci. Part A: Polym. Chem., Vol. 40, 451–458, 2002.<br />
[2]S. Bunker et al., International Journal <strong>of</strong> Adhesion & Adhesives, 23, 29–38,2003.<br />
[3] S.-G. Chu, L.-H. Lee, editor.,New York: Plenum Press, 1991.<br />
[4]A. Zosel, J. Adhes., 18, 265-271, 1998.<br />
78
P24<br />
Renewable aromatic aliphatic copolyesters derived from rapeseed<br />
Stefan Oelmann, Oliver Kreye, Michael A. R. Meier, Institute <strong>of</strong> Organic<br />
Chemistry, Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
stefan-oelmann@versanet.de<br />
Novel (co)polyesters were synthesized from rapeseed as a valuable renewable<br />
resource.[1] The aliphatic monomers were obtained from oleic and erucic acid via thiol-ene<br />
addition. We already prepared monomers and polymers from renewable sources via this<br />
method.[2] Moreover, we -diene monomers <strong>of</strong> ferulic acid,ωdemonstrated the facile<br />
synthesis <strong>of</strong> α, a phenolic acid contains in several natural products, and the -diene<br />
monomers from oleic andωsuccessful copolymerization with α, erucic acid by applying<br />
ADMET and thiol-ene addition polymerization.[3]<br />
Copolyesters with different ratios <strong>of</strong> these monomers were prepared via base-catalyzed<br />
transesterification reactions under neat conditions with different catalysts. 1,5,7-<br />
Triazabicyclo[4.4.0]dec-5-en (TBD), titanium(IV)-isopropoxid (Ti(Oi-Pr)4) and tin(II) 2-<br />
ethylhexanoat (Sn(Oct)2) were tested as catalysts. The best results regarding high<br />
molecular weights were obtained applying TBD as catalyst. Monomers and polymerss<br />
were fully characterized and the polymers were additionally characterized for their thermal<br />
properties. Furthermore, the monomer synthesis was optimized in order to achieve high<br />
yielding and environmentally benign synthetic procedures. Particular focus was put on<br />
applying less toxic reagents, and to minimize chemical waste, in order to meet the<br />
requirements <strong>of</strong> green chemistry.<br />
[1] O. Kreye, S. Oelmann, M. A. R. Meier, Macromol. Chem. Phys. 2013, in preparation.<br />
[2] O. Türünç, M. Firdaus, G. Klein, M. A. R. Meier, Fatty acid derived renewable<br />
polyamides via thiol–ene additions, Green Chem. 2012, 14, 2577-2583.<br />
[3] O. Kreye, T. Tóth, M. A. R. Meier, Copolymers derived from rapeseed derivatives via<br />
ADMET and thiol-ene addition, Eur. Polym. J. 2011, 47, 1804-1816.<br />
79
P25<br />
Influence <strong>of</strong> the double bond configuration on the product composition<br />
<strong>of</strong> Rh-catalyzed maleinisation <strong>of</strong> monounsaturated fatty acids<br />
Steven Eschig, Tunga Salthammer, Claudia Philipp, Fraunh<strong>of</strong>er Institute for Wood<br />
Research, Wilhelm-Klauditz-Institut, Braunschweig, Germany<br />
steven.eschig@wki.fraunh<strong>of</strong>er.de<br />
The synthesis <strong>of</strong> fatty acid based 3,6-disubstituted-1,2,3,6-tetrahydrophthalic anhydrides<br />
(THPA) is a promising opportunity to receive biobased substitutes for monomers like<br />
phthalic anhydride, trimellitic acid and their di-, tetra- or hexahydroderivates, which are<br />
commonly used in polycondensation processes. Especially the 6-membered carbon ring is<br />
<strong>of</strong> great interest because it strongly influences the properties <strong>of</strong> the resulting polyesters, e.<br />
g. the final hardness. The synthesis <strong>of</strong> such rings can be achieved on different pathways.<br />
Well known and frequently studied are the Diels-Alder reactions, where conjugated fatty<br />
acids are used as diene component and converted with a dienophile like maleic anhydride<br />
to give the corresponding 3,6-disubstituted-1,2,3,6-THPA.[1]<br />
Another possibility to synthesize fatty acid based THPA-derivatives is the Rh-catalyzed<br />
maleinisation which has already been investigated for oleic[2] and linoleic acid.[3]<br />
Compared to the Diels-Alder-reaction, it is the main advantage <strong>of</strong> the Rh-catalysis, that it<br />
allows synthesizing 6-membered carbon rings from non-conjugated as well as from<br />
monounsaturated fatty acids. Our previous work has shown that the Rh-catalyzed<br />
maleinisation <strong>of</strong> linoleic acid leads exclusively to the required cyclic substructures.[3] In<br />
contrast to that Behr and Handwerk[2] reported that the maleinisation <strong>of</strong> oleic acids leads<br />
also to acyclic byproducts but without detailed investigations on the selectivity <strong>of</strong> the<br />
different catalysts.<br />
Therefore two different catalysts, Rh(OAc)2 and RhCl3(H2O)3, being already mentioned<br />
by Behr and Handwerk[2] to be suitable, were investigated. The maleinated oleic acid was<br />
esterified with methanol and the resulting product mixtures were analyzed by HPLC. The<br />
corresponding chromatograms (reaction a, reaction c) are shown in Fig. 1. Thereby the<br />
peaks between 30-32 min can be allocated to the cyclic products, whereas the peaks<br />
between 34-36 min belong to the acyclic products.<br />
80
In addition to that it was found that the cis-configurated double bond <strong>of</strong> oleic acid was<br />
isomerized into the thermodynamically favored trans-configuration during the reaction. To<br />
investigate the influence <strong>of</strong> this observed isomerization on the final product composition,<br />
the Rh-catalyzed maleinisation was also carried out with elaidic acid followed by an<br />
esterification with methanol as shown in scheme 1.<br />
All in all it was found that the selectivity towards the cyclic products is much higher for<br />
Rh(OAc)2 than for RhCl3(H2O)3. Furthermore it was observed that the amount <strong>of</strong> elaidic<br />
acid decreases the selectivity towards the cyclic products. These results allow deducing<br />
new insights <strong>of</strong> the ongoing mechanism.<br />
A better understanding <strong>of</strong> this mechanism might give new opportunities to develop new<br />
catalysts which may increase the yield <strong>of</strong> the maleinated products as well as the selectivity<br />
towards the preferred, fatty acid based, cyclic THPAs.<br />
References:<br />
[1] H. J. Schäfer, M. aus dem Kahmen, Fett/Lipid 1998, 100, 227-235<br />
[2] A. Behr, H.-P. Handwerk, Fat Sci. Technol. 1992, 94, 204-208<br />
[3] S. Eschig, C. Philipp, T. Salthammer, Eur. J. Lipid Sci. Technol. 2013, 115, 101- 110<br />
81
P26<br />
α-Arylation <strong>of</strong> saturated fatty acids: a sustainable approach to<br />
renewable monomers?<br />
Nicolai Kolb, Michael A. R. Meier, Institute <strong>of</strong> Organic Chemistry, Karlsruhe<br />
Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
nicolai.kolb@student.kit.edu<br />
With the ongoing limitation <strong>of</strong> fossil resources, it is today’s biggest challenge in chemistry<br />
to develop sustainable approaches for daily-life commodity chemicals. In this context, fatty<br />
acids have been shown to be a promising feedstock for polymer chemistry since they can<br />
be derivatized towards renewable monomers in numerous ways.[1] However, these<br />
derivatizations were mainly carried out with unsaturated fatty acids where the double bond<br />
can be used for many reactions. Saturated fatty acids on the other hand have been barely<br />
used because <strong>of</strong> their limited modification possibilities.<br />
We have recently presented a method for the direct conversion <strong>of</strong> saturated and<br />
unsaturated fatty acid methyl esters towards malonate derivatives by using the α-acidity <strong>of</strong><br />
the ester for the derivatization.[2]<br />
Another approach to use the α-acidity would be the α-arylation reaction.[3] During this<br />
reaction the ester is deprotonated with a strong base to the corresponding enolate, which<br />
can be coupled with aryl halides. This reaction has been intensively studied with shortchain<br />
esters, mainly tert-butyl acetate. However, we found that this arylation reaction is<br />
also possible with saturated fatty acid esters. Furthermore, we tested the arylation reaction<br />
with 1,4-dibromobenzene in order to obtain aryl-bridged diesters for the preparation <strong>of</strong><br />
renewable monomers or gemini-detergents. The synthesis <strong>of</strong> these diesters was<br />
successful for saturated fatty acid esters <strong>of</strong> different chain lengths (C8-C18) with isolated<br />
yields around 60-70%.<br />
Literature:<br />
[1] a) U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O. Metzger, H. J. Schäfer, Angew.<br />
Chem. Int. Ed. 2011, 50, 3854; b) M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem.<br />
Soc. Rev. 2007, 36, 1788.<br />
[2] a) N. Kolb, M. A. R. Meier, Green Chem. 2012, 14, 2429; b) N. Kolb, M. A. R. Meier,<br />
Eur. Poly. J. 2012, accepted.<br />
[3] F. Bellina, R. Rossi, Chem. Rev. 2009, 110, 1082.<br />
82
P27<br />
New transfromations <strong>of</strong> ricinoleic acid derivatives<br />
Manuel Hartweg, Hatice Mutlu, Michael A. R. Meier, Institute <strong>of</strong> Organic Chemistry,<br />
Karlsruhe Institute <strong>of</strong> Technology, Karlsruhe, Germany<br />
manuel.hartweg@gmx.de<br />
In order to replace depleting fossil resources for organic synthesis, and especially for<br />
polymer chemistry, an increasing interest in renewable feedstock becomes more important<br />
in industry as well as research.[1] Inexpensive, readily available commodity oils containing<br />
unusual fatty acids, while having no nutritive value, can be regarded as feedstock <strong>of</strong><br />
choice. With respect to chemical transformations, ricinoleic acid [(12R,9Z)-12-<br />
hydroxyoctadecenoic acid,] – the main component for castor oil – has a broad synthetic<br />
potential for both industrial and academic uses, based primarily upon the unique presence<br />
<strong>of</strong> the hydroxyl group.[2] There are several examples for the utilization <strong>of</strong> ricinoleic acid,<br />
both direct and indirect, or its derivates for the production <strong>of</strong> a broad range <strong>of</strong> functional<br />
molecules, potentially accessible by using efficient and selective (catalytic) methods.[2]<br />
Therefore, the aim <strong>of</strong> this work was to investigate new routes towards further utilization <strong>of</strong><br />
methyl ricinoleate. Along this idea, we focused on the development <strong>of</strong> a more sustainable<br />
methodology for the synthesis <strong>of</strong> conjugated linoleic acids (CLAs) that uses dimethyl<br />
carbonate as a green reagent/solvent. The use <strong>of</strong> TBD as an environmentally friendly base<br />
in the dehydration <strong>of</strong> ricinoleic acid was thus our goal. Our results revealed that in addition<br />
to the desired CLAs, different ricinoleic acid derivatives were obtained. Depending on the<br />
starting derivative <strong>of</strong> ricinoleic acid and the applied reaction conditions, we observed<br />
ricinoleic acid based lactones and lactams as by-products or major products.<br />
References:<br />
[1] U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O. Metzger and H. J. Schäfer, Angew.<br />
Chem. Int. Ed. 2011, 50, 3854.<br />
[2] H. Mutlu and M. A. R. Meier, Eur. J. Lipid Sci. Technol. 2010, 112, 10.<br />
83
P28<br />
Self-metathesis derived renewable 1,4-cyclohexadiene and its potential<br />
applications<br />
Sarah Wald, Michael A. R. Meier, KIT, Institute <strong>of</strong> Organic Chemistry, Karlsruhe, Germany<br />
sarah.wald@student.kit.edu<br />
In the last few years, renewable resources, especially fats and oils, are getting more and<br />
more interesting because <strong>of</strong> decreasing fossil feedstocks and global warming.[1] One<br />
important oil for renewable polymers is chia seed oil, which contains, just like linseed oil,<br />
high amounts <strong>of</strong> α-linolenic acid.[2] The methyl-esters <strong>of</strong> this highly unsaturated oil can be<br />
used for self-metathesis reactions to obtain C18-diesters and volatile products, like 1,4-<br />
cyclohexadiene and 3-hexene.[3] 1,4-Cyclohexadiene can also be synthesized from<br />
soybean oil via olefin metathesis without purification <strong>of</strong> the oil and simple distillation. The<br />
product can, after isomerization to 1,3-cyclohexadiene, be used for polymerization to<br />
renewable polycyclohexadiene.[4] The self-metathesis byproduct, 1,4-cyclohexadiene, can<br />
also be used to prepare monomers for polysulfides and polysulfones, as will be discussed<br />
within this contribution. Therefore, the 1,4-cyclohexadiene was reacted with an excess <strong>of</strong><br />
thioacetic acid in a thiol-ene addition to obtain a mixture <strong>of</strong> regioisomers (S,S'-<br />
cyclohexane-1,4-diyl diethanethioate and S,S'-cyclohexane-1,3-diyl diethanethioate). After<br />
saponification <strong>of</strong> the mixture, the monomers cyclohexane-1,4-dithiol and cyclohexane-1,3-<br />
dithiol, which can be polymerized via thiol-ene-polymerisation with 1,7-octadiene or 1-<br />
octyne to polysulfides, were obtained. After oxidation <strong>of</strong> these polysulfides, the<br />
polysulfones were obtained by simple oxidation with hydrogen peroxide.<br />
References<br />
[1] M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788-1802.<br />
[2] R. Ayerza, W. Coates, Industrial Crops and Products 2011, 34 (2), 1366-1371.<br />
[3] H. Mutlu , R. H<strong>of</strong>säß , R. E. Montenegro, M. A. R. Meier, RSC Adv. 2013.<br />
[4] R. T. Mathers, M. J. Shreve, E. Meyler, K. Damodaran, D. F. Iwig, D. J. Kelley,<br />
Macromol. Rapid Commun. 2011, 32, 1338–1342.<br />
84
P29<br />
Mesoporous niobium-silica materials for the epoxidation <strong>of</strong> vegetable<br />
oil-derived mixtures <strong>of</strong> unsaturated fatty acid methyl esters (FAMEs)<br />
Cristina Tiozzo 1 , Nicoletta Ravasio 1 , Rinaldo Psaro 1 , Dariusz Bogdal 2 , Sylwia<br />
Dworakowska 2 , Matteo Guidotti 1 ,<br />
1 CNR-Institute <strong>of</strong> Molecular Sciences and Technologies, Milan, Italy; 2 Cracow University<br />
<strong>of</strong> Technology, Cracow, Polan<br />
c.tiozzo@istm.cnr.it<br />
Functionalized FAMEs constitute interesting raw materials for obtaining polyurethane materials<br />
suitable for many applications, e.g. coatings as well as flexible and rigid foams. By introducing<br />
hydroxyl groups at the position <strong>of</strong> unsaturated double bonds, it is possible to obtain polyols which<br />
are one <strong>of</strong> the major components in polyurethane synthesis. Vegetable oil-derived unsaturated<br />
FAMEs are therefore viable building blocks for the production <strong>of</strong> polymers from renewable<br />
resources.1,2 Niobium-based silicates have already shown promising performances as<br />
heterogeneous catalysts for liquid-phase oxidation epoxidation <strong>of</strong> alkenes and FAMEs.3,4 These<br />
solids in fact present a high stability and robustness towards metal leaching and hydrolysis. This<br />
feature is a noteworthy advantage for their use in the presence <strong>of</strong> aqueous H2O2 or in watercontaining<br />
media.<br />
The Nb/SiO2 materials studied in this work were prepared by deposition <strong>of</strong> Nb(Cp)2Cl2 onto the<br />
surface <strong>of</strong> different pure silica supports characterized by various textural features following a dry<br />
impregnation (solventless) approach5 (Fig.1). It was thus possible to obtain catalysts with a tailored<br />
metal loading and an optimized surface active site density. The catalysts were used as<br />
heterogeneous catalysts for the selective epoxidation, in the presence <strong>of</strong> aqueous hydrogen<br />
peroxide, <strong>of</strong> a set <strong>of</strong> pure model unsaturated FAMEs as well as <strong>of</strong> FAME mixtures prepared from<br />
food-grade high-oleic rapeseed oil, as such or after selective partial hydrogenation, in order to<br />
maximize the content <strong>of</strong> monounsaturated components.6<br />
OH<br />
OH OH<br />
SiO 2<br />
+ Nb<br />
Cl<br />
Cl<br />
deposition<br />
1) liquid-phase grafting<br />
or<br />
2) dry impregnation<br />
calcination<br />
O 2<br />
500°C<br />
O<br />
Nb<br />
O O O<br />
All the catalysts were particularly active in the first hour <strong>of</strong> reaction. Then, the formation <strong>of</strong> heavy<br />
deposits on the catalyst surface gradually leads to deactivation. The selectivity to epoxide was in<br />
all cases excellent and only minor amounts <strong>of</strong> side-products were found in solution. The catalysts<br />
did not show any leaching <strong>of</strong> active Nb species and proved to be easily recoverable and reusable<br />
after a rapid intermediate calcination step.<br />
Yields in methyl epoxystearate as high as 70% were achieved on pure methyl oleate (4:1 oxidant<br />
to FAME ratio). On rapeseed-derived FAME mixtures (obtained by direct transesterification <strong>of</strong> the<br />
vegetable oil), yields to monoepoxy-FAMEs (epoxystearate and epoxyoleate) up to 55% and 45%<br />
were attained, starting from hydrogenated or non-hydrogenated mixtures, respectively. These data<br />
are among the best results obtained so far for the epoxidation <strong>of</strong> unsaturated FAMEs over solid<br />
oxidic catalysts with hydrogen peroxide.<br />
er<br />
Regione Lombardia (VeLiCa Project) and COST Action CM0903 UBIOCHEM are acknowledged<br />
for financial support.<br />
SiO 2<br />
[1] J.O. Metzger et. al, J. Polym. Sci. Part A: Polym. Chem., 44 (2005) 634<br />
[2] Z.S. Petrovic, I. Cvetkovic, Contemporary Materials, III-1 (2012) 63<br />
[3] M. A. Feliczak-Guzik, I. Nowak, Catal. Today, 142 (2009) 288<br />
[4] Tiozzo C. et al., Eur. J. Lipid Sci. Tech., 115 (2013) 86 [5] A. Gallo, C. Tiozzo, R. Psaro, F. Carniato, M.<br />
Guidotti, J. Catal., 298 (2013) 77<br />
[6] F. Zaccheria, R. Psaro, et al., Eur. J. Lipid Sci. Tech., 114 (2012) 24<br />
85
P30<br />
Isomerizing ethenolysis <strong>of</strong> functionalized olefins<br />
Sabrina Baader, Dominik M. Ohlmann, Lukas J. Gooßen, Fachbereich Chemie,<br />
Organische Chemie, TU Kaiserslautern, Kaiserslautern, Germany<br />
baader@chemie.uni-kl.de<br />
The combination <strong>of</strong> [Pd(μ-Br)(tBu3P)]2 with a Hoveyda-Grubbs II catalyst has been<br />
found to efficiently promote the cross-metathesis between substituted alkenes and<br />
ethylene, while continuously migrating the double bond along the alkenyl chain.[1] When<br />
allylarenes such as the natural products eugenol, safrol or estragol were treated with<br />
this catalyst under ethylene pressure, they were cleanly converted into the<br />
corresponding styrenes along with propylene gas (Scheme 1). This process is <strong>of</strong><br />
particular value in the context <strong>of</strong> renewable chemical synthesis, i.e. for incorporating<br />
naturally occurring allylarenes, some <strong>of</strong> which are available on ton scale, into the<br />
chemical value chain. This conversion <strong>of</strong> the natural product eugenol is a good<br />
example <strong>of</strong> the potential economic impact <strong>of</strong> this transformation, as the corresponding<br />
vinylarene (465 €/100 g) is <strong>of</strong> substantially higher commercial value than the eugenol<br />
starting material (16 €/100 g).<br />
Another application <strong>of</strong> isomerizing metathesis is the efficient conversion <strong>of</strong> technical<br />
quality fatty acids into industrially useful multi-component blends, consisting <strong>of</strong><br />
functionalized olefins with tuneable chain length distributions. [2]<br />
References:<br />
[1] S. Baader, D. M. Ohlmann, L. J. Gooßen, publication submitted.<br />
[2] a) D. M. Ohlmann, L. J. Gooßen, M. Dierker, patent application, 2011. b) D. M.<br />
Ohlmann, N. Tschauder, J.-P. Stockis, K. Gooßen, M. Dierker, L. J. Gooßen, J. Am.<br />
Chem. Soc. 2012, 134, 13716-13729.<br />
86
P31<br />
Synthesis <strong>of</strong> Oleic Acid Based-Polymeric Lattices through Emulsion<br />
and Miniemulsion Polymerization<br />
Alan T. Jensen 1 , Claudia Sayer 2 , Pedro H. H. Araújo 2 , Fabricio Machado 1 ,<br />
University <strong>of</strong> Brasilia, Brasilia, Brazil; 2 Federal University <strong>of</strong> Santa Catarina, Florianópolis<br />
– SC, Brazil<br />
pedro@enq.ufsc.br<br />
The use <strong>of</strong> vegetable oils and their derivatives as precursor monomers in polymerization<br />
reactions has increased each day due to their renewable origin, unlike most materials<br />
obtained from fossil fuel sources. Among them, oleic acid (OA) deserves special attention<br />
due to the high availability and ease <strong>of</strong> chemical modification, mainly when the double<br />
bounds are considered.<br />
This work presents experimental results from copolymerizations <strong>of</strong> acrylated methyl oleate<br />
(AMO) and styrene (Sty) – CAMOSty carried out in both emulsion and miniemulsion<br />
polymerization systems. CAMOSty copolymers produced by emulsion polymerization<br />
exhibited narrow particle size distributions (PSDs), average particle size in the range from<br />
116 nm to 128 nm and conversions lying in the range <strong>of</strong> 96 % to 100 %. Despite the high<br />
conversion achieved during the emulsion reactions, the amount <strong>of</strong> AMO in the monomeric<br />
organic phase is limited to 15 wt.% to avoid reaction medium destabilization and<br />
consequent coagulation <strong>of</strong> the polymer particles possibly due to the low solubility <strong>of</strong> methyl<br />
oleate in aqueous phase that hinders the diffusion <strong>of</strong> AMO from the monomer droplets to<br />
the growing polymer particles. In order to overcome problems with the low solubility and<br />
mass transfer <strong>of</strong> AMO through the aqueous phase a miniemulsion polymerization process<br />
has been employed as the loci <strong>of</strong> polymerization is the monomer droplets. It was observed<br />
that the AMO and Sty can be successfully copolymerized with the additional advantage <strong>of</strong><br />
using higher amounts <strong>of</strong> AMO in the organic polymerizing mixture, which permits the<br />
incorporation AMO fractions higher than 80 wt.%. In the miniemulsion system, high<br />
conversion values were also attained presenting average particle size in the range from<br />
150 nm to 190 nm. Although both processes allow proper copolymerization <strong>of</strong> AMO and<br />
Sty, leading to formation <strong>of</strong> polymer particles with monodisperse PSDs, comparatively,<br />
miniemulsion polymerization process is more attractive due to the high stability <strong>of</strong><br />
polymerization reactions performed with high concentrations <strong>of</strong> AMO.<br />
87
P32<br />
Synthesis <strong>of</strong> polyurethane nanoparticles from renewable resources by<br />
miniemulsion polymerization<br />
Alexsandra Valerio 1 , Sandro R. P. da Rocha 2 , Claudia Sayer 1 , Pedro H. H. Araújo 1 ,<br />
1 Federal University <strong>of</strong> Santa Catarina, Florianópolis – SC, Brazil; 2 Wayne State University<br />
pedro@enq.ufsc.br<br />
Polyurethanes are one <strong>of</strong> the most versatile polymers being the final product easily<br />
tailored, even during the production process. One <strong>of</strong> the reasons for that is the broad<br />
range <strong>of</strong> polyols (e.g., molecular weight, functionalities) that could be employed. Recently,<br />
the development <strong>of</strong> colloidal delivery systems from biodegradable and biocompatible<br />
polyurethanes (PU) has attracted increasing interest as the highly variable synthetic<br />
chemistry <strong>of</strong> PU may be exploited to generate polymers having properties ranging from<br />
very s<strong>of</strong>t elastomers to very rigid plastics.<br />
In this work we will report the preparation <strong>of</strong> PU nanoparticles using<br />
isophoronediisocyanate (IPDI) and different polyols, obtained from renewable resources:<br />
castor oil, glycerol and poly(ɛ-caprolactone) (PCL), through miniemulsion polymerization.<br />
Poly(ethylene glycol) <strong>of</strong> different molar masses (PEG 400, PEG 600, and PEG 1000) were<br />
also added to the reaction medium partially substituting the other polyols. As those<br />
particles were designed for drug delivery, attaching PEG to the outer surface <strong>of</strong> the<br />
particles improves the biodisponibility <strong>of</strong> the polymeric nanoparticles. Results show that<br />
the synthesis <strong>of</strong> polyurethane nanoparticles by miniemulsion polymerization using polyols<br />
from renewable resources is a particularly interesting and facile strategy for the formation<br />
<strong>of</strong> biodegradable and biocompatible nanoparticles, and for the control <strong>of</strong> the chemistry <strong>of</strong><br />
the particle shell.<br />
88
List <strong>of</strong> participants<br />
89
Muhammad Yusuf Abduh<br />
University <strong>of</strong> Groningen<br />
Nijenborgh 4<br />
9747 AG Groningen, Netherlands<br />
p262868@rug.nl<br />
Dr. Khalid A. Alamry<br />
King Abdulaziz University<br />
Aljammah 80203<br />
21589 Jeddah, Saudi Arabia<br />
k_alamry@yahoo.com<br />
Dr. Abdulaziz Ali Alghamdi<br />
King Saud University<br />
King Khaled Street 2455<br />
11451 Riyadh, Saudi Arabia<br />
aalghamdia@ksu.edu.sa<br />
Jessica Allard<br />
NOVANCE<br />
Rue des Rives de l'oise 1<br />
60280 Venette, France<br />
j.allard@novance.com<br />
Dr. Abdulkadir Alli<br />
Department <strong>of</strong> Chemistry<br />
Konuralp 1<br />
81620 Duzce, Turkey<br />
abdulkadiralli@duze.edu.tr<br />
Dr. Ali M. Alsalme<br />
King Saud University<br />
College <strong>of</strong> Science 5<br />
11451 Riyadh, Saudi Arabia<br />
aalsalme@ksu.edu.sa<br />
Thorsten Anders<br />
Fraunh<strong>of</strong>er ICT<br />
Joseph-von-Fraunh<strong>of</strong>erstr. 7<br />
76327 Pfinztal, Germany<br />
thorsten.anders@ict.fraunh<strong>of</strong>er.de<br />
Pr<strong>of</strong>. Dr. Pedro H. H. Araújo<br />
Federal University <strong>of</strong> Santa Catarina<br />
Departamento de Engenharia Quimica e<br />
Engenharia de Alimentos<br />
Cx. Postal 476<br />
88040-970 Florianópolis- SC, Brazil<br />
pedro@eng.ufsc.br<br />
Dr. Matthias Arndt<br />
Clariant Produkte GmbH<br />
Industriepark Höchst D 560<br />
65926 Frankfurt am Main, Germany<br />
matthias.arndt@clariant.com<br />
Pr<strong>of</strong>. Dr. Luc Averous<br />
University <strong>of</strong> Strasbourg<br />
Bio Team<br />
25 rue Becquerel<br />
67087 Strasbourg, France<br />
luc.averous@unistra.fr<br />
Sabrina Baader<br />
TU Kaiserslautern<br />
Fachbereich Chemie, Organische<br />
Chemie<br />
Erwin-Schrödinger-Str. 54<br />
67663 Kaiserslautern, Germany<br />
baader@chemie.uni-kl.de<br />
Pr<strong>of</strong>. Dr. Joel Barrault<br />
CNRS-LACCO<br />
Avenue du Recteur Pineau 40<br />
86022 Poitiers, France<br />
joel.barrault@univ-poitiers.fr<br />
Benjamin Basler<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
bbasler88@gmail.com<br />
Sören Baum<br />
Technical University Hamburg-Harburg<br />
Denickestr. 15<br />
21073 Hamburg, Germany<br />
soeren.baum@tuhh.de<br />
Christian Beck<br />
Wissenschaftszentrum Straubing<br />
Schulgasse 16<br />
94315 Straubing, Germany<br />
c.beck@wz-straubing.de<br />
Dr. Toine Biemans<br />
Worlée Chemie GmbH<br />
Söllerstr.12<br />
21481 Lauenburg, Germany<br />
tbiemans@worlee.de<br />
90
Dr. Ursula Biermann<br />
University <strong>of</strong> Oldenburg<br />
Carl-von-Ossietzky-Str. 9-11<br />
26111 Oldenburg, Germany<br />
ursula.biermann@uni-oldenburg.de<br />
Dr. Rolf Blaauw<br />
Wageningen UR Food & Biobased<br />
Research<br />
Bornse Weilanden 9<br />
6708 WG Wageningen, Netherlands<br />
rolf.blaauw@wur.nl<br />
Pr<strong>of</strong>. Dr. Uwe Bornscheuer<br />
Greifswald University<br />
Institute <strong>of</strong> Biochemistry<br />
Felix-Hausdorff-Str. 4<br />
17487 Greifswald, Germany<br />
bornsche@uni-greifswald.de<br />
Jérôme Boulanger<br />
UCCS Artois<br />
Jean Souvraz SP 18<br />
62307 Lens, France<br />
jerome.boulanger897@laposte.net<br />
Dr. Christian Bruneau<br />
Université de Rennes 1<br />
Avenue du Général Leclerc 263<br />
35042 Rennes, France<br />
christian.bruneau@univ-rennes1.fr<br />
Dr. Katrin Brzonkalik<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute for Process Engineering in Life<br />
Science, Section II: Technical Biology<br />
Engler.Bunte-Ring 1<br />
76131 Karlsruhe<br />
katrin.brzonkalik@kit.edu<br />
Dr. Sylvain Caillol<br />
ENSCM<br />
Ecole Normale 8<br />
34296 Montpellier, France<br />
sylvain.caillol@enscm.fr<br />
Priscilla B. Cardoso<br />
Federal University <strong>of</strong> Santa Catarina<br />
Caixa Postal 476<br />
88010970 Florianopolis, Brazil<br />
Dr. Thibaud Caulier<br />
Solvay<br />
Rue de Ransbeek 310<br />
1120 Brussels, Belgium<br />
thibaud.caulier@solvay.com<br />
Dr. Bret Chrisholm<br />
North Dakota State University<br />
Research Park Drive 1805<br />
58102 Fargo, United States<br />
bret.chrisholm@ndsu.edu<br />
Sunanda Dasgupta<br />
Brandenburg University <strong>of</strong> Technology<br />
Siemens Halske Ring 8<br />
03046 Cottbus, Germany<br />
dasgupta@tu-cottbus.de<br />
Dr. Manfred Diedering<br />
Alberdingk Boley GmbH<br />
Düsseldorfer Str. 39<br />
47829 Krefeld. Germanyowa.kit.edu<br />
m.diedering@alberdingk-boley.de<br />
Dr. Markus Dierker<br />
BASF Personal Care and Nutrition GmbH<br />
Henkelstr. 67<br />
40589 Düsseldorf, Germany<br />
markus.dierker@basf.com<br />
Dr. Christophe Duquenne<br />
Arkema<br />
Rue Jacques Taffanel Alata<br />
60550 Verneul-en-Halatte, France<br />
christophe.duquenne@arkema.com<br />
Sylwia Dworakowska<br />
Cracow University <strong>of</strong> Technology<br />
Warszawska 24<br />
31-155 Cracow, Poland<br />
sylwiadworakowska@gmail.com<br />
Dr. Stephan Enthaler<br />
Technical University <strong>of</strong> Berlin<br />
Str. des 17.Juni 135/ C2<br />
10623 Berlin, Germany<br />
stephan.enthaler@tu-berlin.de<br />
91
Steven Esching<br />
Fraunh<strong>of</strong>er Institute for Wood Research<br />
Wilhelm-Klauditz-Institute<br />
Bienroder Weg 54E<br />
38108 Braunschweig, Germany<br />
steven.esching@wki.fraunh<strong>of</strong>er.de<br />
Dr. Martin Fängewisch<br />
Croda GmbH<br />
Herrenpfad-Süd 33<br />
41334 Nettetal, Germany<br />
matrin.faengewisch@croda.com<br />
Maulidan Firdaus<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
maulidan.firdaus@student.kit.edu<br />
Dr. Jürgen Fischer<br />
ADM Researche GmbH<br />
Seehafenstr. 24<br />
21079 Hamburg, Germany<br />
meike.rademacher@adm.com<br />
Stephanie Flitsch<br />
University <strong>of</strong> Graz<br />
Heinrichstr. 28<br />
8010 Graz, Austria<br />
stephanie.flitsch@uni-graz.at<br />
Marc R. L. Furst<br />
University <strong>of</strong> St. Andrews<br />
North Haugh 1<br />
KY16 9ST St Andrews, United Kingdom<br />
mrlf2@st-andrews.ac.uk<br />
Jakob Gebhard<br />
Institute <strong>of</strong> Technical Biocatalysis<br />
Denickerstr. 15<br />
21071 Hamburg, Germany<br />
jakob.gebhard@tuhh.de<br />
Olga Govedarica<br />
University <strong>of</strong> Novi Sad<br />
Faculty <strong>of</strong> Technolgy<br />
Bul. Cara Lazara 1<br />
21000 Novi Sad, Serbia<br />
oborota@uns.ac.rs<br />
Michael Graß<br />
Evonik Industries AG<br />
Paul-Baumann-Str. 1<br />
45772 Marl, Germany<br />
michael01.grass@evonik.com<br />
Pr<strong>of</strong>. Dr. Dmitry G. Gusev<br />
Wilfrid Laurier University<br />
University Avenue West 75<br />
N2L 3C5 Waterloo, Canada<br />
dgoussev@hotmail.com<br />
Pr<strong>of</strong>. Dr. Frédéric Hapiot<br />
UCCS Artois<br />
Rue Jean Souvraz 00<br />
62307 Lens, France<br />
frederic.hapiot@univ-artois.fr<br />
Manuel Hartweg<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
manuel.hartweg@gmx.de<br />
Dr. Jürgen Herwig<br />
Evonik Instustries AG<br />
Paul-Baumann-Str. 1<br />
45772 Marl, Germany<br />
juergen.herwig@evonik.com<br />
Robert H<strong>of</strong>säß<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
robert.h<strong>of</strong>saess@googlemail.com<br />
Dr. Norbert Holst<br />
Fachagentur Nachwachsende Rohst<strong>of</strong>fe<br />
H<strong>of</strong>platz 1<br />
18267 Gülzow, Germany<br />
n.holst@fnr.de<br />
Thimo Huber<br />
Wissenschaftszentrum Straubing<br />
Schulgasse 16<br />
94315 Straubing, Germany<br />
t.huber@wt-straubing.de<br />
92
Veronika Huber<br />
FH Weihenstephan-Triesdorf<br />
Schulgasse 16<br />
94315 Straubing, Germany<br />
v.huber@wz-straubing.de<br />
Bernd Jakob<br />
University<br />
Gausstr. 20<br />
42097 Wuppertal, Germany<br />
bjakob@uni-wuppertal.de<br />
Pr<strong>of</strong>. George John<br />
The City College <strong>of</strong> CUNY<br />
Department <strong>of</strong> Chemistry<br />
160 Convent Avenue<br />
10031 New York, United States<br />
gglucose@gmail.com<br />
Mandeep Kaur<br />
Thapar University<br />
Bhadson Road 9465236880<br />
147004 Patial, India<br />
mandeepthapar@gmail.com<br />
Pr<strong>of</strong>. Dr. Bert Klein Gebbink<br />
Utrecht University<br />
Universiteitsweg 99<br />
3584 CG Utrecht, Netherlands<br />
r.j.m.kleingebbink@uu.nl<br />
Nicolai Kolb<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
nicolai.kolb@student.kit.edu<br />
Dr. Gunther Kraft<br />
FUCHS Europe Schmierst<strong>of</strong>fe<br />
Friesenheimerstr. 19<br />
68169 Mannheim, Germany<br />
gunther.kraft@fuchs-europe.de<br />
Dr. Oliver Kreye<br />
Karlsruher Institut <strong>of</strong> Technologie<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
oliver_kreye@gmx.de<br />
Dennis Kugele<br />
Karlsruher Institute <strong>of</strong> Technologie<br />
Klosterweg 28<br />
76131 Karlsruhe, Germany<br />
denniskugele@web.de<br />
Dr. Karsten Lange<br />
University <strong>of</strong> Wuppertal<br />
Gaussstr. 20<br />
42097 Wuppertal, Germany<br />
klange@uni-wuppertal.de<br />
Ralph Lange<br />
KIT Karlsruhe<br />
Hagsfelder Allee 10<br />
76131 Karlsruhe, Germany<br />
ralph.lange@student.kit.edu<br />
Rodrigo Ledesma-Amaro<br />
University <strong>of</strong> Salamanca<br />
Palacio Valdés 19 4A<br />
37007 Salamanca, Spain<br />
rodrigoledesma@usal.es<br />
Dr. Dirk Leinweber<br />
Clariant Produkte GmbH<br />
Industriepark Höchst D 560<br />
65926 Frankfurt am Main, Germany<br />
claudia.weichel@clariant.com<br />
Dr. Gerhard Leinz<br />
Alberdingk Boley GmbH<br />
Düsseldorferstr. 53<br />
478229 Krefeld<br />
dr.leinz@alberdingk-boley.de<br />
Audrey AL LLevot<br />
LCPO<br />
Avenue Pey Verland 16<br />
33607 Pessac. France<br />
llevot@enscbp.fr<br />
Cristina Lluch Porres<br />
Rovira i Virgili University<br />
Marcel.li Domingo s/n<br />
43007 Tarrangona, Spain<br />
cristina.llunch@urv.cat<br />
93
Mel Luetkens<br />
Elevance Renewable Science<br />
Davey Road 2501<br />
Woodridge, 60517 Illinois, United States<br />
vera.zaccariello@elevance.com<br />
Wiebke Maassen<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Gotthard-Franz-Straße 3<br />
76131 Karlsruhe, Germany<br />
wiebke.maassen@kit.edu<br />
Chandu S. Madankar<br />
Indian Institute <strong>of</strong> Technology, Delhi<br />
Hauz Khas<br />
110016 New Delhi, India<br />
chandumadankar@gmail.com<br />
Dr. Claudia Martinez<br />
BASF Personal Care and Nutrition GmbH<br />
Henkelstr. 67<br />
40589 Düsseldorf<br />
claudia.a.martinez@basf.com<br />
Sergio Martinez Silvestre<br />
Instituto de Technolgoia Auimicra<br />
Av. Tarongers s/n<br />
46022 Valencia, Spain<br />
sermars4@itq.upv.es<br />
Pr<strong>of</strong>. Dr. Michael A. R. Meier<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
m.a.r.meier@kit.edu<br />
Pr<strong>of</strong>. Dr. Jürgen Metzger<br />
<strong>abiosus</strong> e.V.<br />
Bloherfelder Str. 239<br />
26129 Oldenburg, Germany<br />
metzger@<strong>abiosus</strong>.org<br />
Pr<strong>of</strong>. Dr. Martin Mittelbach<br />
University <strong>of</strong> Graz<br />
Heinrichstr. 28<br />
8010 Graz, Austria<br />
stephanie.flitsch@gmail.com<br />
Dr. Aurélie Morel<br />
Novance<br />
Venette BP 20609<br />
60206 Compiégne, France<br />
a.morel@novance.com<br />
Hermine HNM NSA Moto<br />
Université de Toulouse, INP-Ensiacet<br />
Allée Emilie Monso 4<br />
31030 Toulouse, France<br />
hermine.nsamoto@ensiacet.fr<br />
Zéphirin Mouloungui<br />
INRA<br />
Allé Emile Monso 4<br />
31030 Toulouse, France<br />
zephirin.mouloungui@ensiacet.fr<br />
Pr<strong>of</strong>. Dr. Rolf Mülhaupt<br />
University Freiburg<br />
Institution <strong>of</strong> Macromolecular Chemistry<br />
Stefan-Meier-Str. 31<br />
79104 Freiberg, Germany<br />
rolf.muelhaupt@makro.uni-freiburg.de<br />
Janett Müller<br />
Universität Greifswald<br />
Schuhhagen 28/29<br />
17489 Greifswald, Germany<br />
janett.mueller@uni-greifswald.de<br />
Dr. Hatice Mutlu<br />
Karlsruher Institut <strong>of</strong> Technologie<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
hatice.mutlu@kit.edu<br />
Dr. Anke Neumann<br />
Karlsruher Institut <strong>of</strong> Technologie<br />
Institut für Bio- und Lebensmitteltechnik<br />
Bereich II: Technische Biologie<br />
Engler-Bunte-Ring 1<br />
76135 Karlsruhe, Germany<br />
anke.neumann@kit.edu<br />
Huy Hoang Nguyen<br />
Oleon GmbH<br />
Industriestr. 10<br />
46446 Emmerich am Rhein, Germany<br />
huyhoang.nguyen@oleon.com<br />
94
Tobias Nitsche<br />
Karlsruher Institut <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
tobiasnitsche@aol.com<br />
Stefan Oelmann<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
stefan-oelmann@versanet.de<br />
Dr. Dominik Ohlmann<br />
BASF Personal Care and Nutrition GmbH<br />
Henkelstr. 67<br />
40589 Düsseldorf, Germany<br />
dominik.ohlmann@basf.com<br />
Pr<strong>of</strong>. Dr. Mehmet Musa Özcan<br />
Selcuk University<br />
Selcuklu 1<br />
42031 Konya, Turkey<br />
mozcan@selcuk.edu.tr<br />
An Philippaerts<br />
K. U. Leuven<br />
Kasteelpark Arenberg 23<br />
3001 Heverlee, Belgium<br />
an.philippaerts@biw.kuleuven.be<br />
Dr. Fernando Portela Cabillo<br />
Freundenberg Forschungsdienste<br />
Hoehnerweg 2-4<br />
69469 Weinheim, Germany<br />
fernando.portelacubillo@freundenberg.de<br />
Dr. Yann M. Raoul<br />
SIA<br />
Rue de Monceau CS 60003 11<br />
75378 Paris, Cedex 08, France<br />
y.raoul@prolea.com<br />
Pr<strong>of</strong>. Dr. Herbert Riepl<br />
Hochschule Weihenstephan-Triesdorf<br />
Schulgasse 16<br />
94315 Straubing, Germany<br />
r.karl@wz-straubing.de<br />
Pr<strong>of</strong>. Dr. Yunus Robiah<br />
Universiti Putra Malaysia<br />
Institute od Advanced Technology UPM<br />
43400 Selangor, Malaysia<br />
robiah@eng.upm.edu.my<br />
Philipp Roesle<br />
Universität Konstanz<br />
Universitätsstraße 10<br />
78457 Konstanz, Germany<br />
Philipp.Roesle@uni-konstanz.de<br />
Dr. Sophie M. Sambou<br />
Novance<br />
Rue les Rives de l’Oise<br />
BP 60206 Compiegne Cedex, France<br />
s.sambou@novance.com<br />
Pr<strong>of</strong>. Dr. Hans J. Schäfer<br />
University<br />
Organisch-Chemisches Institut<br />
Correns-Str. 40<br />
48149 Münster, Germany<br />
schafeh@uni-muenster.de<br />
Dr. Benjamin Schäffner<br />
Evonik Industries AG<br />
Paul-Baumann-Str. 1<br />
45772 Marl, Germany<br />
benjamin.schaeffner@evonik.com<br />
Pr<strong>of</strong>. Dr. Ulrich Schörken<br />
FH Köln<br />
Campus Leverkusen<br />
Kaiser-Wilhelm-Allee 1<br />
51368 Leverkusen, Germany<br />
ulrich.schoerken@fh-koeln.de<br />
Alexander Schenzel<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
schenzel.alexander@gmx.de<br />
Dr. Christ<strong>of</strong> Schmitz<br />
Freundenberg Forschungsdienste<br />
Hoehnerweg 2-4<br />
69469 Weinheim, Germany<br />
christ<strong>of</strong>.schmitz@freudenberg.de<br />
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Ansgar Sehlinger<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
ansgar.sehlinger@gmail.com<br />
Stephanie Seidel<br />
Bergische Universität Wuppertal<br />
Gaußstr. 20<br />
42119 Wuppertal, Germany<br />
stephanie.seidel@uni-wuppertal.de<br />
Julian R. Silverman<br />
City College <strong>of</strong> New York<br />
609 W 135 th Street 20<br />
10031 New York, United States<br />
jsilverman@gc.cuny.edu<br />
Pr<strong>of</strong>. Dr. Snezana Sinadinovic-Fiser<br />
University <strong>of</strong> Novi Sad<br />
Faculty <strong>of</strong> Technology<br />
Bul. Cara Lazara 1<br />
21000 Novi Sad, Serbia<br />
ssfiser@uns.ac.rs<br />
Susanne Solleder<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
susanne.solleder@student.kit.edu<br />
Dr. Claudia Stoer<br />
BASF Personal Care and Nutrition GmbH<br />
Henkelstr. 67<br />
40589 Düsseldorf, Germany<br />
claudia.stoer@basf.com<br />
Alexander Studentschnig<br />
Karl-Franzens University Graz<br />
Institute <strong>of</strong> Organic/Bioorganic Chemistry<br />
Heinrichstr. 28/II<br />
8010 Graz, Austria<br />
alexander.studentschnig@uni-graz.at<br />
Pr<strong>of</strong>. Dr. Christoph Syldatk<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Technical Biology<br />
Egnler-Bunte-Ring<br />
76135 Karlsruhe, Germany<br />
christoph.syldatk@kit.edu<br />
Dr. Oguz Türünc<br />
Ghent University<br />
Department <strong>of</strong> Organic Chemistry<br />
Polymer Chemistry Research Group<br />
Krijgslaan 281<br />
9000 Ghent, Belgium<br />
turunc.oguz@gmail.com<br />
Yushin Takahashi<br />
Kao Chemicals GmbH<br />
Kupferstr. 1<br />
46446 Emmerich, Germany<br />
yushin.takahashi@kaochemicals.de<br />
Elke Theeuwes<br />
Ecover Co-ordination Center NV<br />
Steenovenstraat 1A<br />
2390 Malle, Belgium<br />
theeuwes.elke@ecover.com<br />
Dr. Cristina Tiozzo<br />
CNR-ISTM<br />
Via Venezian 21<br />
20133 Milan, Italy<br />
c.tiozzo@istm.cnr.it<br />
Peter J. Tollington<br />
Cargill BV<br />
Jan van Galenstraat 4<br />
3115 JG Schiedam, Netherlands<br />
peter_tollington@cargill.com<br />
Maike Unverferth<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
maike.unverferth@kit.edu<br />
Richard Vendamme<br />
Nitto Europe N.V.<br />
Eikelaartsraat 22<br />
3600 Genk, Belgium<br />
richard.vendamme@neu.fr<br />
Dr. Pierre Villeneuve<br />
CIRAD<br />
2 Place Viala 2<br />
34060 Montpellier, France<br />
villeneuve@cirad.fr<br />
96
Hanna Wagner<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
hannawagner91@gmx.de<br />
Sarah Wald<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
sarah.wald@student.kit.edu<br />
Matthias Winkler<br />
Karlsruhe Institute <strong>of</strong> Technology<br />
Institute <strong>of</strong> Organic Chemistry<br />
Fritz-Haber-Weg 6<br />
76131 Karlsruhe, Germany<br />
svm-winkler@t-online.de<br />
Stefanie Wolf<br />
Clariant Produkte GmbH<br />
Ludwig-Hermann-Str. 100<br />
86368 Gersth<strong>of</strong>en, Germany<br />
stefanie1.wolf@clariant.com<br />
Motonori Yamamoto<br />
BASF SE<br />
GMT/ B-B001<br />
Carl-Bosch Str. 38<br />
67056 Ludwigshafen, Germany<br />
montori.yamamoto@basf.com<br />
Dr. Aalbert Zwijnenburg<br />
Johnson Matthey Chemicals GmbH<br />
Wardstr. 17<br />
46446 Emmerich am Rhein, Germany<br />
bart.zwijenburg@matthey.com<br />
97